Om2c00556 Si 001

Supporting Information
Properties and catalytic activity of Hoveyda-Grubbs-type

catalysts with an S→Ru coordination bond in a six-membered
chelate ring
Pavel A. Kumandin,a Alexandra S. Antonova,a Roman A. Novikov,b Kirill A.
Vasilyev,a Marina A. Vinokurova,a Mikhail S. Grigoriev,c Anton P. Novikov,c Daria
K. Polianskaia,a Kirill B. Polyanskii,a,* Fedor I. Zubkova,*
a
Organic Chemistry Department, Faculty of Science, Peoples’ Friendship University of Russia (RUDN University),
6 Miklukho-Maklaya St., Moscow 117198, Russian Federation
e-mail: Fedor I. Zubkov – [email protected]
e-mail: Kirill B. Polyanskii − [email protected]
b
N. D. Zelinsky Institute of Organic Chemistry of RAS, 47 Leninsky Prospect, Moscow 119991, Russian Federation
c
Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, 31 Leninsky Prospect,
bld. 4, Moscow 119071, Russian Federation
TABLE OF CONTENTS
1. General information............................................................................................................................ 2
2. Synthetic procedures ........................................................................................................................... 3
2.1 Ligand synthesis .............................................................................................................................. 3
2.2 Synthesis of trans-complexes 11 ..................................................................................................... 6
2.3 Synthesis of cis-complexes 12 ......................................................................................................10
2.4 Activity of 11 in RCM reactions...................................................................................................14
2.6 Activity of 12 in RCM reactions with N,N-diallyltosylamide ....................................................16
2.7 Activity of 12 in RCM reactions under photochemical activation ............................................17
2.8 Polymerization of norborn-5-ene-2,3-dicarboxylic acid dibutyl ester (NBBA) catalyzed by
complexes 11d,e,g,h ...................................................................................................................................18
3. NMR studies of complexes 11 and 12 ..............................................................................................20
3.1 Isomerization of 11 in TCE-d2 and CDCl3 ..................................................................................20
4. X-ray experiments .................................................................................................................................34
4.1 General information......................................................................................................................34
4.2. Tables and Figures ........................................................................................................................34
5. UV/Vis initiation kinetics ..................................................................................................................71
6. References ..............................................................................................................................................73
7. Copies of NMR spectra of compounds 9, 11, 12 .................................................................................74
S-1
1. General information
All experiments with ruthenium derivatives except metathesis reactions were performed
under an inert atmosphere of dry argon, using standard Schlenk techniques, dry and oxygen-free
solvents. Toluene, THF and heptane were distilled over sodium under an argon atmosphere, 1,2-
DCE was dried over P2O5 and distilled under argon atmosphere. For catalytic experiments dry
CHCl3 and toluene were used everywhere. All the starting reagents were purchased from Sigma-
Aldrich, and used as received. TLC analyses were performed by using Merck pre-coated silica gel
(0.2 mm) aluminium-backed plats (n-hexane for styrenes, n-hexane : ethyl acetate = 3:1 for
catalysts).
1
H, 13C And 31P NMR spectra for compounds 9a−h were recorded on Jeol JNM-ECA 600
spectrometer (600.1 MHz for 1H, 50.9 MHz for 13C and 242.9 MHz) using residual solvent signals
(7.26/77.0 ppm for 1H/13C CDCl3 and 5.36/53.4 ppm for CH2Cl2 and 17.3 ppm for methylene
diphosphonic acid (MDP)) or SiMe4 as an internal standard. Chemical shifts are given relative to
SiMe4 or referenced to the residual solvent signals.
1 13
H, C NMR spectra of the Ru–S carbene complexes 11a−h and 12a−c, 12e−h were
recorded on 300 MHz (300.1, 75.5 MHz, respectively) or 400 MHz (400.1, 100.6 MHz,
respectively) spectrometers in CD2Cl2, TCE-d2 (1,1,2,2-tetrachloroethane-d2), and CDCl3
solutions using 0.05% SiMe4 as the external or internal standard. Determinations of structures and
stereochemistry of the obtained ruthenium complexes and assignments of 1H, 13
C signals were
made with the aid of 2D COSY, NOESY, edited-HSQC, and HMBC spectra. Temperature for all
experiments was set as –10 °C, 0 °C, or 25 °C dependence on stability of the studied complexes.
Kinetic NMR studies (series of 1H spectra) of the isomerization process of trans-isomers
11 to cis-isomers 12 were recorded at +70 °C or +80 °C in TCE-d2 (1,1,2,2-tetrachloroethane-d2),
or at +60 °C in CDCl3, over a time period of 1.5–42 h depending on the rate of isomerization of
the complexes.
13
C{1H} And 13C-dept135-{1H} NMR spectra with {1H}-decoupling were recorded using
90° "garp" composite pulse with 0.19 W power for broadband decoupling instead of commonly
used "waltz16" composite pulse. If "waltz16" composite pulse was still used, its power should be
at least 1 W for effective full decoupling of the 1JH–C coupling constant for CH=Ru signals at 290–
320 ppm, and a sufficient cooling by strong air flow should be used to avoid an overheating of a
sample. The same situation is for recording of 1H–13C HSQC and edited-HSQC spectra, however
in this case, 90° "garp" composite pulse with 1 W power for broadband {13C}-decoupling in the
detected 1H-channel should be used in a combination with sufficient cooling of a sample by a
strong air flow. 1H NMR spectra, as well as 2D 1H–1H COSY, TOCSY, NOESY, and 1H–13C
S-2
HMBC spectra, were recorded in conventional mode. All necessary pulses and pulse sequences
were used from Bruker library.
IR spectra were obtained in KBr pellets or in thin films using an Infralum FT-801 IR-
Fourier spectrometer. HR-LDI mass spectra of the Grubbs catalysts 11 and 12 were recorded using
a ToF mass spectrometer Bruker autoflex speed, equipped with a solid-state UV-laser of 355 nm
and operated in positive reflectron mode. Solutions of the analytes (2 mg/mL) in CH2Cl2 were
deposited on steel targets (MTP 384 ground steel; Bruker Daltonics Inc., Germany) and air-dried.
Microanalyses were performed for C, H, N on an Eurovector EA 3000 (CHNS) elemental analysis
system and were within ±0.4% of theoretical values.
2. Synthetic procedures
2.1 Ligand synthesis
Scheme S1. Synthesis of 2-vinylbenzylchloride 8
N,N-Вimethyl-2-vinylbenzylamine 7 was prepared according to a previously reported

procedure.1
Methyl chloroformate (5.05 g, 0.0465 mol, 1.5 equiv.) was added dropwise to a mixture of
N,N-dimethyl-2-vinylbenzylamine 7 (5.00 g, 0.031 mol, 1 equiv.) and K2CO3 (6.51 g, 0.0465 mol,
1.5 equiv.) in dry THF (50 mL) cooled to −78 ℃ under an argon atmosphere. The mixture was
stirred at this temperature for 30 min and for further 12 h at ambient temperature. Then it was
poured into cold water (50 mL) and extracted with ether (3 × 50 mL). The organic phase was
washed with brine (100 mL) and dried over anhydrous Na2SO4, concentrated under reduced
pressure and purified by flash-chromatography, using hexane as eluent. The product 8 was
obtained as colourless oil (4.30 g, 0.028 mol, 91%).
Scheme S2. Synthesis of benzylidene ligands 9
S-3
Suitable thiol (0.011 mol, 1.1 equiv.) was added to a solution of NaOH (0.62 g, 0.011 mol,
1.1 equiv.) in MeOH (40 mL), followed by addition of 2-vinylbenzylchloride 8 (1.52 g, 0.010 mol,
1 equiv.). The mixture was refluxed for 4−12 h. After full consumption of starting materials
(monitored by TLC, eluent n-hexane) the reaction mixture was poured into water (50 mL),
extracted with ether (2 × 50 mL), the ethereal layer was washed with 10% NaOH solution (100
mL) and brine (100 mL). Then it was dried over anhydrous MgSO4 and concentrated under
reduced pressure, affording crude styrene 9, which was further purified by flash chromatography
(SiO2, hexane).
2-Vinylbenzyl butyl sulfide (9a)

Pale-yellow oil, 1.84 g, 0.0089 mol, 89%.
1
Н NMR (600.17 MHz, CDCl3, 23 °C) δ, ppm: 7.51 (1H, d, J = 7.6 Hz, H-3), 7.24-7.18 (3H, m,
H-4, H-5, H-6), 7.13 (1H, dd, J = 10.6, 17.2 Hz, H-1-Vinyl), 5.70 (1H, dd, J = 1.1, 17.2 Hz, H-2-
Vinyl-trans), 5.35 (1H, dd, J = 1.1, 10.6 Hz, H-2-Vinyl-cis), 3.76 (2H, s, CH2S), 2.47 (1H, t, J =
7.3 Hz, SCH2-CH2), 1.58-1.53 (2H, m, 2-Bu), 1.41-1.35 (2H, m, 3-Bu), 0.89 (3H, t, J = 7.3 Hz,
Me-Bu).
13
C NMR (75.5 MHz, CDCl3, 23 °C) δ, ppm: 137.0, 135.5, 134.3, 130.2, 127.7, 127.5, 126.2,
116.1, 34.1, 31.7, 31.6, 22.1, 13.8.
IR (KBr): 3177, 3175, 3148, 2970, 2961, 996, 858, 744, 718, 708, 602 cm-1.
HRMS [M+H]+ calcd. for C13H19S 207.1202, found 207.1195.
2-Vinylbenzyl isobutyl sulfide (9b)
1
Н NMR (600.17 MHz, CDCl3, 23 °C) δ, ppm: 7.52 (1H, d, J = 7.3 Hz, H-6), 7.24-7.20 (3H, m,
H-3, H-4, H-5), 7.13 (1H, dd, J = 11.1, 17.2 Hz, H-1-Vinyl), 5.70 (1H, dd, J = 1.0, 17.2 Hz, H-2-
Vinyl-trans), 5.35 (1H, dd, J = 1.0, 11.1 Hz, H-2-Vinyl-cis), 3.74 (2H, s, CH2S), 2.36 (2H, d, J =
6.8 Hz, CH2-iPr), 1.82 (1H, hept, J = 6.8 Hz, CHMe2), 0.97 (6H, d, J = 6.8 Hz, CHMe2).
13
116.1, 41.3, 34.6, 28.5, 22.2.
IR (KBr): 3177, 3172, 3150, 2971, 2970, 996, 718, 707, 601 cm-1.
2-Vinylbenzyl isopropyl sulfide (9c)
1
Н NMR (600.17 MHz, CDCl3, 23 °C) δ, ppm: 7.51 (d, J = 7.6 Hz, H-6), 7.25-7.19 (3H, m, H-3,
H-4, H-5), 7.13 (1H, dd, J = 10.6, 17.7 Hz, H-1-Vinyl), 5.70 (1H, br.d, J = 17.7 Hz, H-2-Vinyl-
trans), 5.35 (1H, br.d, J = 10.6 Hz, H-2-Vinyl-cis), 3.79 (2H, s, CH2S), 2.92 (1H, hept, J = 6.6
Hz, CHMe2), 1.29 (6H, d, J = 6.6 Hz, CHMe2).
S-4
13
116.1, 35.2, 32.9, 23.4.
IR (KBr): 3180, 3179, 3174, 3148, 2970, 2966, 2961, 1011, 995, 706, 610 cm-1.
2-Vinylbenzyl tert-butyl sulfide (9d)
1
Н NMR (600.17 MHz, CDCl3, 23 °C) δ, ppm: 7.50-7.49 (1H, m, H-3), 7.30-7.19 (3H, m, H-4, H-
5, H-6), 7.14 (1H, dd, J = 11.1, 17.2 Hz, H-1-Vinyl), 5.72 (1H, dd, J = 1.5, 17.2 Hz, H-2-Vinyl-
trans), 5.36 (1H, dd, J = 1.5, 11.1, H-2-Vinyl-cis), 3.80 (2H, s, CH2S), 1.40 (9H, s, t-Bu).
13
116.0, 43.0, 30.7.
IR (KBr): 3180, 3179, 3146, 3033, 2971, 997, 714, 703, 602 cm-1.
2-Vinylbenzyl 4-methoxyphenyl sulfide (9e)
1
Н NMR (600.17 MHz, CDCl3, 23 °C) δ, ppm: 7.49 (1H, dd, J = 7.5 Hz, H-6), 7.27-7.25 (2H, m,
H-2-C6H4-OMe, H-6-C6H4-OMe), 7.23-7.20 (1H, m, H-4), 7.13 (1H, td, J = 1.51, 7.57 Hz, H-5),
7.02-7.01 (1H, m, H-6), 6.80-6.78 (2H, m, H-3-C6H4-OMe, H-5-C6H4-OMe), 5.68 (1H, dd, J =
1.5, 17.2 Hz, H-2-Vinyl-trans), 5.33 (1H, dd, J = 1.5, 11.1, H-2-Vinyl-cis), 4.04 (2H, s, CH2S),
3.78 (3H, s, OMe).
13
128.3, 127.7, 126.1, 125.9, 116.2, 114.5, 55.4, 39.1.
IR (KBr): 3152, 2940, 1492, 1277, 967, 760, 757, 749, 707 cm-1.
HRMS [M+H]+ calcd. for C16H17SO 257.0995, found 257.0990.
2-Vinylbenzyl phenyl sulfide (9f)
1
Н NMR (600.17 MHz, CDCl3, 23 °C) δ, ppm: 7.51 (1H, br.d, J = 7.6 Hz, H-6), 7.32-7.30 (2H,
m, H-2-Ph, H-6-Ph), 7.27-7.15 (6H, m, H-3, H-4, H-5, H-3-Ph, H-4-Ph, H-5-Ph), 7.09 (1H, dd, J
= 11.1, 17.7 Hz, H-1-Vinyl), 5.70 (1H, dd, J = 1.5, 17.7 Hz, H-2-Vinyl-trans), 5.34 (1H, dd, J =
1.5, 11.1, H-2-Vinyl-cis), 4.15 (2H, s, CH2S).
13
C NMR (75.5 MHz, CDCl3, 23 °C) δ, ppm: 137.2, 136.6, 134.1, 130.3. 130.2, 129.0, 127.9,
126.6, 126.2, 116.5, 37.1
IR (KBr): 3176, 3151, 1387, 1163, 998, 971, 711, 700, 601 cm-1.
2-Vinylbenzyl 4-methoxyphenyl sulfide (9g)
S-5
Golden crystals. 2.52 g, 0.0093 mol, 93%.
1
Н NMR (600.17 MHz, CDCl3, 23 °C) δ, ppm: 8.12-8.10 (2H, m, H-3-C6H4-NO2, H-5-C6H4-
NO2), 7.53 (1H, br.d, H-6), 7.35-7.33 (2H, m, H-2-C6H4-NO2, H-6-C6H4-NO2), 7.31-7.22 (2H, m,
H-3, H-4, H-5), 7.06 (1H, ddd, J = 0.9, 10.5, 17.6 Hz, H-1-Vinyl), 5.73 (1H, br.d, J = 17.6 Hz, H-
2-Vinyl-trans), 5.40 (1H, br.d, J = 10.6, H-2-Vinyl-cis), 4.28 (2H, s, CH2S).
13
128.1, 126.8, 126.5, 124.0, 117.3, 35.1.
IR (KBr): 3175, 3168, 1385, 1276, 1077, 1048, 755, 720, 691 cm-1.
HRMS [M+H]+ calcd. for C15H14NO2S 207.1202, found 207.1195.
2-Vinylbenzyl 2-naphtyl sulfide (9h)
Beige crystals. 2.73 g, 0.0099 mol, 99%.
1
Н NMR (600.17 MHz, CDCl3, 23 °C) δ, ppm: 8.41 (1H, d, J = 8.1 Hz, H-8- Naph), 7.85 (1H, J
= 8.1 Hz, H-4-Naph), 7.76 (1H, J = 8.1 Hz, H-5-Naph), 7.54-7.49 (3H, m, H-2-Naph, H-6-Naph,
H-7-Naph), 7.37 (1H, t, J = 7.6 Hz, H-3-Naph), 7.23 (1H, t, J = 7.4 Hz, H-6), 7.12-7.04 (3H, m,
H-3, H-4, H-5), 5.69 (1H, d, J = 17.2 Hz, H-2-Vinyl-trans), 5.32 (1H, d, J = 11.0 Hz, H-2-Vinyl-
cis), 4.19 (2H, s, CH2S).
13
129.7, 128.5, 127.8, 127.7, 126.5, 126.2, 126.0, 125.5, 125.2, 116.3, 37.2.
IR (KBr): 3179, 3150, 1388, 1163, 998, 979, 712, 700, 603 cm-1.
2.2 Synthesis of trans-complexes 11
Scheme S3. Synthesis of trans-complexes 11a−h
Ruthenium complex 10 (500 mg, 0.53 mmol, 1.0 equiv) was suspended in heptane (15 mL)
under an argon atmosphere in a Schlenk flask and the mixture was heated to 80 °C with continuous
stirring. Then styrene 9 (0.58 mmol, 1.1 equiv) was added in an argon stream and the flask was
sealed with a screw cap. The mixture was heated at 80 °C for 1 h, and then cooled to −20 °C. The
precipitate was filtered off and washed with hexane (3 × 5 mL) and methanol cooled to −20 ℃ (3
× 3 mL) to give green powder of pure catalysts 11a−h after drying under vacuum.
S-6
[1,3-Bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene]{2-
[(butylsulfanyl)methyl]benzylidene}dichlororuthenium (11a)
Green powder, 238 mg, 0.36 mmol, 67%, m.p. 188.2−189.7 ℃.
1
Н NMR (300.13 MHz, CD2Cl2, 30 °C) δ, ppm: 18.86 (1H, s, CH=Ru),
7.50-7.45 (1H, m, H-4-C6H4), 7.10-6.88 (6H, m, H-Mes and H-3,5-C6H4),
6.48 (1H, d, J = 7.5 Hz, H-6-C6H4), 4.36 (3H, d, J = 12.1 Hz, S-CH2-C6H4
and S-CH2-PrA), 4.03 (4H, s, NCH2CH2N), 2.31 (18H, s, Me-Mes), 1.69 (2H, m, S-CH2-CH2-Et),
1.12-0.93 (2H, m, S-CH2-CH2-CH2-Me), 0.90-0.51(3H, m, S-CH2-CH2-CH2-CH3).
C NMR (75.5 MHz, CD2Cl2, 30 °C) δ, ppm: 315.4, 148.5, 145.8, 139.8, 139.0, 137.9, 136.5,
13
135.8, 134.5, 133.7, 132.9, 132.1, 132.0, 130.0, 129.5, 129.4, 129.2, 128.7, 30.5, 29.1, 22.0, 21.4,
20.3, 13.8.
IR (KBr): 2953, 1612, 1595, 1489, 1407, 1307, 1261, 1185, 1032, 862, 813, 785, 742, 641, 575
cm-1.
MALDI-ToF MS [M-Cl]+ calcd. for C33H42ClN2RuS 635.1795, found 635.1787.
[1,3-Bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene](dichloro)(2-{[(2-
methylpropyl)sulfanyl]methyl}benzylidene)ruthenium (11b)
1
Н NMR (300.13 MHz, CD2Cl2, 30 °C) δ, ppm: 18.25 (1H, s, CH=Ru), 7.53
(1H, t, J = 7.6 Hz, H-4-C6H4), 7.21 (1H, s, H-Mes), 7.16 (1H, t, J = 7.6 Hz,
H-5-C6H4), 7.12 (1H, s, H-Mes), 7.08 (1H, d, J = 7.6 Hz, H-3-C6H4), 7.00 (1H, s, H-Mes), 6.42
(1H, d, J = 7.6 Hz, H-6-C6H4), 6.33 (1H, s, H-Mes), 4.54 (1H, d, J = 12.1 Hz, SCH2-A), 4.31-4.21
(1H, m, H-4, H-5), 4.12-4.04 (1H, m, NCH2CH2N), 3.96-3.76 (2H, m, NCH2CH2N), 3.59 (1H, d,
J = 12.1 Hz, SCH2-B), 3.31 (1H, dd, J = 5.6, 14.0 Hz, CH2-iPr), 2.92 (3H, s, Me-Mes), 2.81 (3H,
s, Me-Mes), 2.40 (3H, s, Me-Mes), 2.35 (3H, s, Me-Mes), 2.30 (3H, s, Me-Mes), 1.92-1.79 (1H,
m, CHMe2), 1.53 (3H, s, Me-Mes), 1.02 (3H, J = 6.1 Hz, CHMe-A), 0.98 (3H, J = 6.1 Hz, CHMe-
B), 0.73 (1H, dd, J = 9.8, 14.0 Hz, CH2B-iPr).
13
135.5, 134.1, 133.1, 131.0, 130.5, 130.3, 130.0, 129.9, 128.8, 128.2, 54.2, 53.8, 53.4, 53.1, 52.7,
51.4, 42.8, 39.3, 26.3, 22.4, 20.8, 20.7, 20.0, 19.1, 18.8, 17.8.
IR (KBr): 2943, 1607, 1595, 1408, 1244, 1172, 1028, 854, 816, 776, 744, 643, 573 cm-1.
S-7
[1,3-Bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene](dichloro){2-
[(propan-2-ylsulfanyl)methyl]benzylidene}ruthenium (11c)
1
(1H, br.t, J = 7.6 Hz, H-4-C6H4), 7.18-7.12 (2H, m, H-3,5-C6H4), 7.10 (2H,
s, H-3,5-Mes), 7.00 (2H, s, H-3,5-Mes), 6.50 (1H, d, J = 7.6 Hz, H-6-C6H4),
4.88 (1H, d, J = 11.9 Hz, SCH2-A), 4.12 (4H, s, NCH2CH2N), 3.61(1H, d, J = 11.9 Hz, SCH2-B),
3.23 (1H, hept, SCHMe2), 2.58 (6H, s, Me-4-Mes), 2.40 (12H, s, Me-2,6-Mes), 1.23 (3H, d, J =
6.7 Hz, SCHMe2), 0.54 (3H, d, J = 6.7 Hz, SCHMe2).
13
128.7, 128.6, 127.7, 54.2, 53.8, 53.4, 53.1, 52.7, 51.7, 38.6, 35.6, 21.5, 20.9, 20.7, 19.2.
IR (KBr): 2946, 1611, 1595, 1403, 1246, 1184, 1029, 858, 820, 770, 735, 639, 567 cm-1.
[1,3-Bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene]{2-[(tert-
butylsulfanyl)methyl]benzylidene}dichlororuthenium (11d)
1
(1H, t, J = 7.7 Hz, H-4), 7.17-7.12 (2H, m, H-3,5), 7.04 (4H, very br. s, H-
Mes), 6.53 (1H, d, J = 7.7 Hz, H-6), 4.13 (4H, s, NCH2CH2N), 3.42 (2H,
very br. s, S-CH2), 2.58 (12H, very br. s, Me-2,6-Mes), 2.41 (6H, s, Me-4-Mes), 1.06 (9H, s, t-Bu-
S).
13
131.9, 129.4, 129.2, 128.6, 128.1, 51.8, 51.2, 47.1, 32.7, 29.5, 20.7, 20.1, 18.3.
IR (KBr): 2941, 1612, 1584, 1401, 1253, 1180, 1031, 850, 816, 775, 727, 633, 573 cm-1.
[1,3-Bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene](dichloro)(2-
{[(4-methoxyphenyl)sulfanyl]methyl}benzylidene)ruthenium (11e)
1
H NMR (300.1 MHz, CD2Cl2, −10 °C) δ, ppm: 18.87 (1H, s,
CH=Ru), 7.47 (1H, t, J = 7.6 Hz, H-4), 7.18 (1H, t, J = 7.1 Hz, H-
5), 7.02-7.00 (6H, m, H-2,6, H-Mes), 6.93 (1H, d, J = 7.1 Hz, H-3),
6.64 (2H, d, J = 8.1 Hz, H-3,5-C6H4-OMe), 6.51 (1H, d, J = 8.1 Hz, H-6), 4.89 (1H, br.d, J = 12.1
S-8
Hz, SCH2-A), 4.10-4.06 (5H, m, SCH2-B, NCH2CH2N), 3.73 (3H, s, OCH3), 2.67 (3H, s, Me-
Mes), 2.48 (3H, s, Me-Mes), 2.43 (3H, s, Me-Mes), 2.40 (3H, s, Me-Mes), 2.37 (3H, s, Me-Mes),
2.22 (3H, s, Me-Mes).
13
С NMR (75.5 МHz, CD2Cl2, −10 °C) δ, ppm: 315.1, 209.7, 159.9, 149.4, 140.0, 139.3, 138.7,
137.8, 137.7, 136.7, 134.3, 136.1, 132.2, 132.0, 129.7, 129.2, 128.9, 120.8, 114.3, 55.6, 51.8, 51.2,
41.7.
IR (KBr): 2958, 1614, 1604, 1414, 1246, 1185, 1039, 861, 824, 785, 732, 631, 574 cm-1.
MALDI-ToF MS [M-Cl]+ calcd. for C36H40ClN2ORuS 685.1588, found 685.1590.
[(phenylsulfanyl)methyl]benzylidene}ruthenium (11f)
1
H NMR (300.1 MHz, CD2Cl2, 30 °C) δ, ppm: 18.83 (1H, s, CH=Ru),
7.48 (1H, t, J = 7.6 Hz, H-4), 7.28 (1H, t, J = 7.0 Hz, H-5), 7.17-7.11
(4H, m, H-Ph), 7.06-7.01 (2H, m, H-3, H-Ph), 7.00 (4H, s, H-Mes), 6.50
(1H, d, J = 7.6 Hz, H-6), 5.20 (1H, d, J = 12.0 Hz, SCH2-A), 4.12-4.03 (5H, m, SCH2-B,
NCH2CH2N), 2.70 (3H, s, Me-Mes), 2.50 (3H, s, Me-Mes), 2.41 (6H, s, Me-Mes), 2.37 (3H, s,
Me-Mes), 2.14 (3H, s, Me-Mes).
С NMR (176.1 МHz, CD2Cl2, 30 °C) δ, ppm: 314.5, 209.6, 149.6, 139.8, 139.4, 138.9, 138.8,
13
138.2, 137.8, 136.8, 134.2, 132.3, 131.5, 131.4, 131.2, 129.8, 129.7, 128.5, 129.2, 128.9, 52.3,
51.2, 40.0, 34.3.
IR (KBr): 2956, 1606, 1605, 1410, 1256, 1176, 1029, 860, 818, 790, 737, 639, 568 cm-1.
[1,3-Bis(2,4,6-trimethylphenyl)imidazolidin-2-
ylidene](dichloro)(2-{[(4-
nitrophenyl)sulfanyl]methyl}benzylidene)ruthenium (11g)
1
H NMR (300.1 МHz, CD2Cl2, −10 °C) δ, ppm: 18.73 (1H, s,
CH=Ru), 7.96 (2H, d, J = 9.1 Hz, H-2,5-C6H4-NO2), 7.54 (1H, t, J
= 7.6 Hz, H-4), 7.21 (1H, t, J = 7.6 Hz, H-5), 7.13-7.85 (7H, m, 2,6-C6H4-NO2, H-Mes, H-3), 6.50
(1H, d, J = 8.1 Hz, H-5), 5.34 (1H, d, J = 12.0 Hz, SCH2-A), 4.10-4.01 (5H, m, SCH2-B,
NCH2CH2N), 2.70 (3H, s, Me-Mes), 2.52 (3H, s, Me-Mes), 2.40 (3H, s, Me-Mes), 2.37 (3H, s,
Me-Mes), 2.28 (3H, s, Me-Mes), 2.09 (3H, s, Me-Mes).
13
138.9, 137.7, 136.6, 134.1, 132.5, 129.8, 129.4, 129.0, 123.6, 52.4, 51.1, 37.6, 31.8.
S-9
IR (KBr): 2947, 1620, 1580, 1406, 1252, 1170, 1032, 855, 824, 782, 725, 638, 570 cm-1.
MALDI-ToF MS [M-Cl]+ calcd. for C35H37ClN3O2RuS 700.1333, found 700.1339.
ylidene](dichloro){2-[(naphthalen-2-
ylsulfanyl)methyl]benzylidene}ruthenium (11h)
1
H NMR (300.1 МHz, CDCl3, −10 °C) δ, ppm: 19.02 (1H, s, CH=Ru),
7.83 (1H, s, H-1-Naphthyl), 7.80-7.74 (2H, m, H-6,7-Naphthyl), 7.58
(1H, d, J = 8.5 Hz, H-3-Naphthyl), 7.52-7.45 (3H, m, H-4,5,8-Naphthyl), 7.19-7.05 (7H, m, H-
3,4,5, H-Mes), 6.59 (1H, d, J = 7.6 Hz, H-6), 5.36 (1H, d, J = 11.6 Hz, SCH2-A), 4.30 (1H, d, J
= 11.6 Hz, SCH2-B), 4.15-4.12 (4H, m, NCH2CH2N), 2.79-2.18 (18H, m, Me-Mes).
С NMR (75.5 МHz, CDCl3, −10 °C) δ, ppm: 315.4, 210.5, 150.0, 139.4, 138.8, 137.9, 137.0,
13
134.1, 133.2, 132.8, 132.3, 131.5, 129.7, 129.6, 129.3, 129.2, 128.9, 128.8, 128.3, 128.0, 127.7,
127.2, 126.7, 126.4, 52.3, 51.2, 39.2, 31.8, 22.9, 21.3, 20.6, 20.3, 18.7, 18.4, 14.5.
IR (KBr): 2954, 1612, 1589, 1413, 1245, 1171, 1033, 852, 824, 783, 729, 648, 565 cm-1.
2.3 Synthesis of cis-complexes 12
Scheme S4. Synthesis of cis-complexes 12a−c, 12e−h
Ruthenium complex 10 (500 mg, 0.53 mmol, 1.0 equiv) was dissolved in 1,2-
dichloroethane (6 mL) under an argon atmosphere in a Schlenk flask and the mixture was heated
to 80 °C with continuous stirring. Then styrene 9 (0.58 mmol, 1.1 equiv) was added in an argon
stream and the flask was sealed with a screw cap. The mixture was heated at 105−110 °C for 3−4
h. The solvent was evaporated under reduced pressure and the residue was suspended in hexane
(10 mL). The precipitate was filtered off and washed with hexane (3 × 5 mL) and then with
methanol cooled to −20 ℃ (3 × 3 mL) to give teal powder of pure catalysts 12a−c, 12e−h after
drying under vacuum.
S-10
[1,3-Bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene]{2-
[(butylsulfanyl)methyl]benzylidene}dichlororuthenium (12a)
Teal powder, 316 mg, 0.47 mmol, 89%, m.p. 205.3−207.1 ℃.
1
7.54 (1H, t, J = 7.5 Hz, H-4-C6H4), 7.20 (1H, s, H-Mes), 7.16 (1H, t, J
= 7.9 Hz, H-5-C6H4), 7.12 (1H, s, H-Mes), 7.10 (1H, d, J = 7.7 Hz, H-
3-C6H4), 7.00 (1H, s, H-Mes), 6.41 (1H, d, J = 7.5 Hz, H-6-C6H4), 6.32 (1H, s, H-Mes), 4.50 (1H,
d, J = 12.1 Hz, S-CH2A-C6H4), 4.28−4.15 (1H, m, NCH2CH2N-A), 4.11-4.03 (1H, m,
NCH2CH2N-A), 3.95-3.74 (2H, m, NCH2CH2N-B), 3.64 (1H, d, J = 12.0 Hz, S-CH2B-C6H4), 3.15-
3.06 (1H, m, SCH2Pr-A), 2.90 (3H, s, Me-Mes), 2.79 (3H, s, Me-Mes), 2.39 (3H, s, Me-Mes), 2.31
(3H, s, Me-Mes), 1.71-1.62 (2H, m, SCH2CH2Et), 1.48 (3H, s, Me-Mes), 1.41 (2H, sextet, J = 7.5,
14.8 Hz, SCH2CH2CH2CH3), 1.00 (3H, t, J = 7.1 Hz, Me).
13
136.1, 135.5, 135.2, 133.8, 133.0, 130.9, 130.6, 130.2, 129.9, 129.8, 128.8, 128.2, 39.6, 35.8, 30.8,
22.6, 20.8, 20.7, 19.8, 19.1, 18.6, 18.2, 17.7, 13.8.
IR (KBr): 2956, 1605, 1583, 1408, 1263, 1181, 1028, 859, 825, 783, 746, 633 cm-1.
[1,3-Bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene](dichloro)(2-
{[(2-methylpropyl)sulfanyl]methyl}benzylidene)ruthenium (12b)
1
7.45 (1H, br.t, J = 7.0 Hz, H-4-C6H4), 7.10 (2H, br.t, J = 7.0 Hz, H-3,5-
C6H4), 6.99 (4H, s, H-Mes), 6.47 (1H, d, J = 6.9 Hz, H-6-C6H4), 4.08-4.05
(3H, m, SCH2-i-Pr-A, SCH2), 4.03 (4H, s, NCH2CH2N), 2.53, 2.36 and 2.19 (18H, s, Me-Mes),
0.74 (6H, d, J = 37.0 Hz, SCH2CHMe2).
13
137.9, 137.7, 137.0, 134.6, 132.0, 129.5, 129.3, 129.0, 128.8, 52.2, 51.2, 39.9, 35.7, 26.4, 22.1,
21.9, 21.4, 20.4.
IR (KBr): 2945, 1607, 1599, 1405, 1256, 1181, 1038, 864, 823, 781, 747, 646, 566 cm-1.
S-11
[(propan-2-ylsulfanyl)methyl]benzylidene}ruthenium (12c)
1
7.49 (1H, t, J = 7.6 Hz, H-4-C6H4), 7.21 (1H, t, J = 7.3 Hz, H-3-C6H4),
7.16 (1H, s, H-Mes), 7.11 (1H, t, J = 7.6 Hz, H-3-C6H4), 7.02 (1H, s, H-
Mes), 6.98 (1H, s, H-Mes), 6.72 (1H, d, J = 7.0 Hz, H-6-C6H4), 6.21 (1H, s, H-Mes), 4.28 (1H, d,
J = 13.7 Hz, SCH2A), 3.97-3.85 (4H, m, NCH2CH2N), 3.44 (1H, d, J = 14.6 Hz, SCH2B), 2.88
(3H, s, Me-Mes), 2.71 (3H, s, Me-Mes), 2.62-2.52 (1H, m, CHMe2), 2.39 (3H, s, Me-Mes), 2.38
(3H, s, Me-Mes), 2.19 (3H, s, Me-Mes), 1.71 (3H, s, Me-Mes), 1.16 (3H, d, J = 6.1 Hz, CHMeA),
1.07 (3H, d, J = 6.1 Hz, CHMeB).
13
137.0, 135.8, 134.9, 133.8, 130.5, 130.2, 129.8, 129.5, 129.4, 128.8, 128.2, 39.7, 34.5, 31.6, 29.7,
22.6, 20.8, 20.6, 20.0, 18.0.
IR (KBr): 2953, 1613, 1600, 1418, 1240, 1176, 1025, 870, 823, 785, 731, 634, 569 cm-1.
methoxyphenyl)sulfanyl]methyl}benzylidene)ruthenium (12e)
1
H NMR (300.1 MHz, CD2Cl2, 25 °C) δ, ppm: 18.38 (1H, s,
HC=Ru), 7.77−7.73 (2H, m, H-2,6C6H4-OMe), 7.57 (1H, dt, J =
0.8, 7.5 Hz, H-4), 7.21 (1H, t, J = 7.5 Hz, H-5), 7.14 (1H, s, H-Mes), 7.09 (1H, br.d, J = 7.5 Hz,
H-3), 7.05 (1H, s, H-Mes), 6.83-6.78 (2H, m, H-3,5-C6H4-OMe), 6.52 (1H, d, J = 7.5 Hz, H-6),
6.37 (1H, br.s, H-Mes), 5.99 (1H, br.s, H-Mes), 5.49 (1H, d, J = 12.4 Hz, SCH2-A), 4.29-4.04 (2H,
m, NCH2CH2N-A), 3.89 (3H, s, OMe), 3.87-3.81 (2H, m, NCH2CH2N-B), 2.90 (3H, s, Me-Mes),
2.83 (3H, s, Me-Mes), 2.36 (3H, s, Me-Mes), 2.17 (3H, s, Me-Mes), 1.93 (3H, s, Me-Mes), 1.71
(3H, s, Me-Mes).
С NMR (75.5 МHz, CDCl3, 25 °C) δ, ppm: 197.0, 215.7, 160.7, 146.2, 139.2, 138.2, 136.2,
13
136.0, 135.8, 134.9, 133.7, 133.1, 130.6, 130.2, 130.1, 130.0, 129.8, 129.8, 129.6, 128.1, 122.2,
114.1, 55.3, 54.2, 53.8, 53.4, 53.1, 52.7, 52.3, 51.2, 46.5, 20.8, 20.7, 19.8, 19.1, 18.2, 17.9.
S-12
IR (KBr): 2951, 1617, 1599, 1412, 1241, 1182, 1031, 867, 822, 779, 742, 632, 573 cm-1.
MALDI-ToF MS [M-Cl]+ calcd. for C36H40ClN2ORuS 685.1588, found 685.1593.
ylidene](dichloro){2-
[(phenylsulfanyl)methyl]benzylidene}ruthenium (12f)
1
H NMR (300.1 МHz, CD2Cl2, 30 °C) δ, ppm: 18.39 (1H, s, CH=Ru),
7.81 (2H, dd, J = 1.2, 7.4 Hz, H-2,6-Ph), 7.58 (1H, dt, J = 1.2, 7.6 Hz,
H-4), 7.45 (1H, br.t, J = 7.4 Hz, H-4-Ph), 7.30 (2H, br.t, J = 7.4 Hz, H-3,5-Ph), 7.20 (1H, br.t, J
= 7.5 Hz, H-5), 7.14 (1H, s, H-Mes), 7.09 (1H, br.d, J = 7.6 Hz, H-3), 7.07 (1H, s, H-Mes), 6.55
(1H, br.d, J = 7.6 Hz, H-6), 6.38 (1H, br.s, H-Mes), 5.91 (1H, br.s, H-Mes), 5.53 (1H, d, J = 12.3
Hz, SCH2-A), 4.29-4.09 (2H, m, NCH2CH2N-A), 3.90-3.79 (2H, m, NCH2CH2N-B), 3.60 (1H, d,
J = 12.3 Hz, SCH2-B), 2.92 (3H, s, Me-Mes), 2.84 (3H, s, Me-Mes), 2.36 (3H, s, Me-Mes), 2.15
(3H, s, Me-Mes), 1.91 (3H, s, Me-Mes), 1.71 (3H, s, Me-Mes).
13
135.9, 135.8, 133.8, 133.5, 133.1, 131.4, 130.6, 130.3, 130.0, 129.9, 129.6, 129.1, 128.7, 128.2,
52.3, 51.2, 46.2, 20.8, 20.7, 19.8, 19.1, 18.2, 17.8.
IR (KBr): 2957, 1612, 1581, 1405, 1251, 1175, 1035, 860, 816, 785, 722, 637, 565 cm-1.
nitrophenyl)sulfanyl]methyl}benzylidene)ruthenium (12g)
1
H NMR (300.1 МHz, CD2Cl2, 30 °C) δ, ppm: 18.27 (1H, s,
CH=Ru), 8.08 (2H, d, J = 8.6 Hz, 3,5-C6H4-NO2), 7.95 (2H, d, J
= 8.6 Hz, 2,6-C6H4-NO2), 7.59 (1H, t, J = 7.4, 14.5 Hz, H-4), 7.25-7.10 (4H, m, H-3, H-5, H-
Mes), 6.51 (1H, d, J = 7.6 Hz, H-6), 6.37 (1H, br.s, H-Mes), 5.94 (1H, br.s, H-Mes), 5.47 (1H, d,
J = 11.9 Hz, SCH2-A), 5.37 (1H, d, J = 3.3 Hz, SCH2-B), (2H, m, NCH2CH2N-A), 3.84-3.71 (2H,
m, NCH2CH2N-B), 2.92 (3H, s, Me-Mes), 2.81 (3H, s, Me-Mes), 2.36 (3H, s, Me-Mes), 2.12 (3H,
s, Me-Mes), 1.94 (3H, s, Me-Mes), 1.64 (3H, s, Me-Mes).
13
138.6, 138.4, 135.9, 135.5, 135.4, 134.5, 133.4, 133.1, 131.0, 130.9, 130.3, 129.9, 129.6, 128.6,
123.4, 52.3, 51.4, 46.0, 21.1. 21.0, 20.1, 19.5, 18.3, 18.0.
IR (KBr): 2948, 1606, 1585, 1420, 1254, 1173, 1033, 856, 820, 779, 745, 630 cm-1.
S-13
MALDI-ToF MS [M-Cl]+ calcd. for C35H37ClN3O2RuS 700.1333, found 700.1326.
ylidene](dichloro){2-[(naphthalen-2-
ylsulfanyl)methyl]benzylidene}ruthenium (12h)
1
H NMR (300.1 МHz, CD2Cl2, 30 °C) δ, ppm: 18.42 (1H, s,
CH=Ru), 8.52 (1H, s, H-1-Naphthyl), 7.94-7.91 (1H, m, H-3-
Naphthyl), 7.81-7.78 (3H, m, H-6,7-Naphthyl, H-Mes), 7.63-7.55 (3H, m, H-4,5,8-Naphthyl), 7.24
(1H, t, J = 7.4 Hz, H-4), 7.16 (1H, s, H-Mes), 7.12 (1H, d, J = 7.6 Hz, H-5), 6.98 (1H, br.s, H-
Mes), 6.58 (1H, d, J = 7.4 Hz, H-6), 6.40 (1H, br.s, H-Mes), 5.58 (1H, d, J = 12.4 Hz, SCH2-A),
4.22-4.09 (2H, m, NCH2CH2N-A), 3.90-3.79 (2H, m, NCH2CH2N-B), 3.68 (1H, d, J = 12.4 Hz,
SCH2-B), 2.94 (3H, s, Me-Mes), 2.85 (3H, s, Me-Mes), 2.37 (3H, s, Me-Mes), 1.90 (3H, s, Me-
Mes), 1.74 (3H, s, Me-Mes), 1.60 (3H, s, Me-Mes).
С NMR (176.1 МHz, CDCl3, 25 °C) δ, ppm: 297.1, 215.5, 146.2, 139.5, 138.2, 136.2, 135.9,
13
135.8, 134.5, 133.8, 133.3, 133.2, 133.1, 130.7, 130.3, 130.2, 130.0, 129.7, 129.5, 129.2, 128.8,
128.2, 128.1, 127.5, 127.3, 126.6, 54.1, 53.8, 53.4, 53.0, 45.8, 20.8, 20.1, 19.8, 19.1, 18.2, 17.9.
IR (KBr): 2953, 1620, 1604, 1412, 1253, 1189, 1026, 855, 818, 786, 726, 632, 568 cm-1.
Figure S1. 11a (left) and 12a (right) complexes.
2.4 Activity of 11 in RCM reactions
Complexes 11 (0.004 mmol, 0.5 mol%, 5 mL solution in dry CHCl3) were added to a
solution of diene 15, 17 or 19 (0.20 g, 0.8 mmol, 1 equiv.) in dry CHCl3 (15 mL). The reaction
mixture was stirred at 25 °C or 60 °C for 90 min. An aliquote (1 mL) was sampled every 15 min
S-14
and 0.1 mL of ethyl vinyl ether (10% solution in THF) was added to. Solvents were removed under
reduced pressure and a RCM-substrate/product mixture was examined by 1H NMR.
Scheme S5. RCM reactions of 15, 17, 19 promoted by 11 complexes in CHCl3
100
80
11a (R1 = nBu)

11b (R1 = iBu)
Conversion, %
60
11c (R1 = iPr)
11d (R1 = tBu)
40 11e (R1 = 4-MeOC6H4)
11f (R1 = Ph)
11g (R1 = 4-NO2C6H4)
20 11h (R1 = 2-Naphthyl)
N-Morph
HG-II
0 HG-II, DCM
0 20 40 60 80
Time, min
Figure S2. Progress of the RCM reaction of 15 promoted by 11, N-Morph and HG-II in CHCl3
at 25 °C. Dashed line demonsrates activity of HG-II in DCM.
100
80
11e, r.t, (R1 = 4-MeOC6H4)

11f, r.t, (R1=Ph)
Conversion, %
60
11g, r.t, (R1 = 4-NO2C6H4)
11h, r.t, (R1 = 2-Naphthyl)
40 N-Morph, r.t
11e, D, (R1 = 4-MeOC6H4)

20 11f, D, (R1=Ph)
11g, D, (R1 = 4-NO2C6H4)
11h, D, (R1 = 2-Naphthyl)
0 N-Morph, D
0 20 40 60 80
Time, min
Figure S3. Progress of the RCM reaction of 17 promoted by 12e−h and N-Morph in CHCl3.
Dashed lines demonsrate activity of complexes at 25 °C, bold lines – at reflux.
S-15
100
Conversion, % 80
60 11e (R1 = 4-MeOC6H4)

11f (R1 = Ph)
11g (R1 = 4-NO2C6H4)
40
11h (R1 = 2-Naphthyl)
N-Morph
20
0
0 50 100 150
Time, min
Figure S4. Progress of the RCM reaction of 19 promoted by 11e−h and N-Morph in CHCl3 at
25 °C.
2.6 Activity of 12 in RCM reactions with N,N-diallyltosylamide
Scheme S6. RCM reaction of 13 promoted by 12c, 12e−h complexes in boiling PhMe.
Complex 12c, 12e−h (0.004 mmol, 0.5 mol%, 5 mL solution in dry PhMe) was added to a
solution of N,N-diallyltosylamide 13 (0.20 g, 0.8 mmol, 1 equiv.) in dry toluene (15 mL). The
reaction mixture was heated to reflux and stirred for 30 min. An aliquote (1 mL) was sampled
every two min and 0.1 mL of ethyl vinyl ether (10% solution in THF) was added to. Solvents were
removed under reduced pressure and a 13/14 ratio was examined by 1H NMR.
S-16
100
80
12c (R1 = iPr)

Conversion, %
60 12e (R1 = 4-MeOC6H4)

12f (R1 = Ph)
12g (R1 = 4-NO2C6H4)
40
20
0
0 5 10 15 20 25 30
Time, min
Figure S5. Progress of the RCM reaction of 15 promoted by 12c, 12e−h in PhMe.
2.7 Activity of 12 in RCM reactions under photochemical activation
Scheme S7. RCM reaction of 13 promoted by 12e−h complex under photochemical activation at
25 °C.
Complex 12e−h (0.004 mmol, 0.5 mol%, 5 mL solution in dry PhMe) was added to a
solution of N,N-diallyltosylamide 13 (0.20 g, 0.8 mmol, 1 equiv.) in dry PhMe (15 mL). The
reaction vessel was placed in an UV reactor and stirred for 180 min. An aliquote (1 mL) was
sampled every 15 min and 0.1 mL of ethyl vinyl ether (10% solution in THF) was added to.
Solvents were removed under reduced pressure and a 13/14 ratio was examined by 1H NMR.
S-17
100
80
12e (R1 = 4-MeOC6H4)

Conversion, %
60 12f (R1 = Ph)

12g (R1 = 4-NO2C6H4)
40
20
0
0 50 100 150
Time, min
Figure S6. Progress of the RCM reaction of 15 promoted by 12e−h in CHCl3 under photochemical
activation.
2.8 Polymerization of norborn-5-ene-2,3-dicarboxylic acid dibutyl ester (NBBA)

catalyzed by complexes 11d,e,g,h
Scheme S8. ROMP polymerization of NBBA2 promoted by 11d−h catalysts.
Сomplex 11d,e,g,h (0.04 mmol, 0.001 mol%, 2 mL solution in dry CHCl3) was added to
thermostated (25 °C) and stirred (600−1000 rpm) NBBA (10 g, 0.05 mol, 1 equiv.). Temperature
changes were measured every 5 seconds by a thermocouple until a plateau was reached. As a
result, solidification of the monomer was observed.
S-18
100
80
Temperature, ˚C
11d (R1 = tBu)

60 11e (R1 = 4-MeOC6H4)
11g (R1 = 4-NO2C6H4)
N-Morph
40
HG-II
Et2N
20
0 20 40 60 80 100 120
Time, s
Figure S7. Isotherm of the ROMP reaction of NBBA promoted by 11d,e,g,h, Morph, HG-II and
Et2N.
Figure S8. Pictures of polyNBBA obtained in the presence of catalyst 11h (left) and Et2N (right).
S-19
3. NMR studies of complexes 11 and 12
3.1 Isomerization of 11 in TCE-d2 and CDCl3
Scheme S9. Isomerization of complexes 11b,c,e, 11f−h in TCE-d2
100
80
11→12 conversion, %
60 11b→12b at 70 ℃ (R1= iBu)

11с→12c at 70 ℃ (R1= iPr)
11e→12e at 70 ℃ (R1= 4-MeOC6H4)
40 11f→12f at 70 ℃ (R1= Ph)
11g→12g at 70 ℃ (R1= 4-NO2C6H4)
11h→12h at 70 ℃ (R1= 2-Naphthyl)
20
11h→12h at 80 ℃ (R1= 2-Naphthyl)
0
0 100 200 300 400 500
Time, min
Figure S9. NMR kinetics of isomerisation of complexes 11b,c,e, 11f−h in TCE-d2.
S-20
S-21
Figure S10. Isomerization of 11b to 12b (+70 °C, TCE-d2).
Time points (from top to bottom): 0 – 5 – 32 – 55 – 120 – 226 min
S-22
Figure S11. Isomerization of 11c to 12c (+60 °C, CDCl3)
Time points (from top to bottom): 0 – 83 – 261 – 579 – 1344 min
S-23
Figure S12. Isomerization of 11c to 12c (+70 °C, TCE-d2)
Time points (from top to bottom): 0 – 8 – 30 – 54 – 101 – 206 – 452 – 2482 min
S-24
S-25
Figure S13. Isomerization of 11e to 12e (+70 °C, TCE-d2)
S-26
Figure S14. Isomerization of 11f to 12f (+70 °C, TCE-d2)
S-27
S-28
Figure S15. Isomerization of 11g to 12g (+70 °C, TCE-d2)
S-29
Figure S16. Isomerization of 11h to 12h (+60 °C, CDCl3)
Time points (from top to bottom): 0 – 6 – 12 – 59 – 87 min
S-30
S-31
Figure S17. Isomerization of 11h to 12h (+70 °C, TCE-d2)
Time points (from top to bottom): 0 – 8.5 – 15 – 30 – 60 – 120 min
S-32
Figure S18. Isomerization of 11h to 12h (+80 °C, TCE-d2)
S-33
4. X-ray experiments
4.1 General information
X-ray diffraction experiments were carried out on a Bruker KAPPA APEX II area-detector
diffractometer. Unit cell parameters were refined over the entire data set.3 Absorption corrections
were introduced using the SADABS program.4 The structures were solved by a direct method
using the SHELXS-2014 program (Sheldrick, 2008)5 and refined by full-matrix least squares on
F2 in the anisotropic approximation for all non-hydrogen atoms (SHELXL-2018 (Sheldrick,
2015).6) The H atoms were objectively located from the difference Fourier synthesis and refined
in an idealized geometry with isotropic temperature factors equal to 1.2Ueq(C) for CH2- and CH-
groups, and 1.5Ueq(C) for CH3-groups, the orientation of CH3-groups was refined. Structure 7 was
refined as an inversion twin. Tables and pictures for structures were generated using Olex2.7 In
structures 11g, 11e, 11h solvent molecules were strongly disordered and therefore they were
removed using the SQUEEZE routine of PLATON,8 and the structure was then refined again using
the data generated. Crystal data, data collection and structure refinement details are summarized
in Tables S1 and S2. Bond lengths and bond angles for molecules 11d,e,g,h and 12a,b,e−h are
given in Tables S3−S22, corresponding molecular structures are shown in Figures S19−S29.
A range of the obtained complexes include solvent molecules in their crystal cells. In 12b the
asymmetric fragment contains two complexes with ruthenium and three solvate molecules of
dichloromethane. The asymmetric fragments in 11d and 12h contain, in addition to one ruthenium
complex, a disordered toluene molecule (11d) or one dichloromethane molecule (12f). In 12g, in
addition to the ruthenium complex molecule, the asymmetric fragment contains a crystallization
water molecule. The asymmetric fragment in structure 12e contains two molecules of the
ruthenium cis-complex and six molecules of the solvent dichloromethane.
X-ray diffraction experiments were performed at the Center for Shared Use of Physical
Methods of Investigation at the Frumkin Institute of Physical Chemistry and Electrochemistry,
RAS.
Atomic coordinates for 11d,e,g,h, 12a,b and 12e−h have been deposited with the
Cambridge Crystallographic Data Centre, CCDC numbers are 2195497−2195506. The
supplementary crystallographic data can be obtained free of charge from the Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
4.2. Tables and Figures
Table S1. Crystal data and structure refinement for complexes 12a, 12b, 11d, 12f and 12g
S-34
Compound 12a 12b 11d 12f 12g
CCDC deposition
2195502 2195506 2195504 2195505 2195500
number
R1 nBu iBu tBu Ph 4-nitrophenyl
C33H42N2SCl2 C34.5H45N2SCl5 C73H92N4S2Cl4 C36H40N2SCl4 C35H37N3O2SCl2
Empirical formula
Ru Ru Ru2 Ru Ru
Formula weight 670.71 798.10 1433.56 775.63 735.70
Temperature/K 296(2) 100(2) 150(2) 296(2) 296(2)
Crystal system monoclinic monoclinic trigonal monoclinic monoclinic
Space group P21/c P21/n R-3 P21/c P21/c
a/Å 11.6951(2) 15.653(4) 26.8778(15) 12.7429(4) 12.3026(4)
b/Å 15.7656(3) 29.157(8) 26.8778(15) 15.7213(5) 15.8717(5)
c/Å 18.1941(4) 16.509(3) 25.223(3) 19.0887(7) 18.0533(5)
α/° 90 90 90 90 90
β/° 105.313(1) 101.895(9) 90 109.158(1) 105.033(1)
γ/° 90 90 120 90 90
Volume/Å3 3235.53(11) 7373(3) 15780(2) 3612.3(2) 3404.50(18)
Z 4 8 9 4 4
ρcalcg/cm3 1.377 1.438 1.358 1.426 1.435
μ/mm-1 0.738 0.871 0.686 0.815 0.714
F(000) 1392.0 3288.0 6714.0 1592.0 1512.0
0.4 × 0.32 × 0.4 × 0.2 × 0.23 × 0.21 × 0.16 × 0.14 ×
Crystal size/mm3 0.4 × 0.3 × 0.12
0.28 0.03 0.18 0.08
MoKα (λ = MoKα (λ = MoKα (λ = MoKα (λ = MoKα (λ =
Radiation
0.71073) 0.71073) 0.71073) 0.71073) 0.71073)
2Θ range for data 8.174 to
8.38 to 55 2.38 to 52.924 8.098 to 55 8.212 to 55
collection/° 59.998
-14 ≤ h ≤ 15, - -22 ≤ h ≤ 17, - -27 ≤ h ≤ 33, - -16 ≤ h ≤ 16, - -15 ≤ h ≤ 15, -
Index ranges 20 ≤ k ≤ 20, - 41 ≤ k ≤ 41, - 33 ≤ k ≤ 33, - 20 ≤ k ≤ 17, - 20 ≤ k ≤ 20, -23
23 ≤ l ≤ 23 12 ≤ l ≤ 23 31 ≤ l ≤ 31 24 ≤ l ≤ 24 ≤ l ≤ 22
Reflections collected 30431 63282 78677 43919 26704
7395 [Rint = 21264 [Rint = 8277 [Rint =
7250 [Rint = 7781 [Rint =
Independent 0.0368, 0.1591, 0.0505,
0.1125, Rsigma = 0.0355, Rsigma =
reflections Rsigma = Rsigma = Rsigma =
0.0641] 0.0376]
0.0331] 0.2285] 0.0492]
Data/restraints/parame
7395/0/358 21264/18/779 7250/323/476 8277/0/403 7781/0/408
ters
Goodness-of-fit on F2 1.018 1.001 1.030 1.021 1.013
Final R indexes R1 = 0.0306, R1 = 0.0851, R1 = 0.0488, R1 = 0.0449, R1 = 0.0349,
[I>=2σ (I)] wR2 = 0.0717 wR2 = 0.1892 wR2 = 0.1011 wR2 = 0.0973 wR2 = 0.0785
Final R indexes [all R1 = 0.0451, R1 = 0.1970, R1 = 0.0875, R1 = 0.0904, R1 = 0.0572,
data] wR2 = 0.0790 wR2 = 0.2384 wR2 = 0.1172 wR2 = 0.1175 wR2 = 0.0899
Largest diff. peak/hole
0.51/-0.37 2.21/-1.78 1.28/-0.58 0.85/-0.49 0.77/-0.61
/ e Å-3
Table S2. Crystal data and structure refinement for complexes 11g, 12e, 11e, 12h and 11h
Compound 11g 12e 11e 12h 11h
CCDC deposition
2195498 2195499 2195501 2195503 2195497
number
4-methoxy- 4-methoxy-
R1 4-nitrophenyl 2-naphthyl 2-naphthyl
phenyl phenyl
C38.5H45N3O2SCl C39H46N2OSCl8 C39.5H48N2OSCl C39H40N2SCl2 C46H56N2SCl2
Empirical formula
2Ru Ru 2Ru Ru Ru
Formula weight 785.80 975.51 770.83 740.76 840.95
Temperature/K 296(2) 120(2) 296(2) 296(2) 100(2)
Crystal system monoclinic monoclinic monoclinic orthorhombic monoclinic
S-35
Space group P21/n P21 P21/n Pbca Cc
a/Å 15.1227(7) 14.0162(15) 15.3675(3) 14.9666(5) 21.2769(14)
b/Å 8.5417(3) 15.6298(17) 8.5657(2) 21.3493(8) 21.6612(14)
c/Å 29.4748(13) 20.328(3) 29.2733(7) 22.6893(8) 8.5444(5)
α/° 90 90 90 90 90
β/° 92.192(2) 102.848(5) 92.465(1) 90 94.476(3)
γ/° 90 90 90 90 90
Volume/Å3 3804.6(3) 4341.8(9) 3849.78(15) 7249.8(4) 3926.0(4)
Z 4 4 4 8 4
ρcalcg/cm3 1.372 1.492 1.330 1.357 1.423
μ/mm-1 0.644 0.935 0.632 0.667 0.625
F(000) 1628.0 1992.0 1604.0 3056.0 1760.0
0.42 × 0.22 × 0.4 × 0.3 × 0.42 × 0.04 ×
Crystal size/mm3 0.4 × 0.18 × 0.08 0.2 × 0.1 × 0.06
0.16 0.24 0.04
MoKα (λ = MoKα (λ = MoKα (λ = MoKα (λ = MoKα (λ =
Radiation
0.71073) 0.71073) 0.71073) 0.71073) 0.71073)
2Θ range for data
8.156 to 54.996 8.226 to 54.99 8.362 to 54.998 8.304 to 55 8.45 to 55
collection/°
-19 ≤ h ≤ 19, -11 -18 ≤ h ≤ 16, - -18 ≤ h ≤ 19, - -19 ≤ h ≤ 17, -27 ≤ h ≤ 27,
Index ranges ≤ k ≤ 10, -38 ≤ l 20 ≤ k ≤ 20, - 11 ≤ k ≤ 11, -38 -27 ≤ k ≤ 27, -28 ≤ k ≤ 27,
≤ 37 25 ≤ l ≤ 26 ≤ l ≤ 38 -29 ≤ l ≤ 26 -11 ≤ l ≤ 10
Reflections collected 34548 37153 45364 60681 20417
8289 [Rint = 8106 [Rint =
8695 [Rint = 19475 [Rint = 8786 [Rint =
Independent 0.1168, 0.0791,
0.1044, Rsigma = 0.0754, Rsigma = 0.0373, Rsigma =
reflections Rsigma = Rsigma =
0.1125] 0.1395] 0.0369]
0.0778] 0.1200]
Data/restraints/param
8695/0/403 19475/19/950 8786/0/394 8289/0/412 8106/2/412
eters
Goodness-of-fit on F2 0.951 0.983 1.020 1.146 0.969
Final R indexes R1 = 0.0546, R1 = 0.0592, R1 = 0.0353, R1 = 0.0806, R1 = 0.0547,
[I>=2σ (I)] wR2 = 0.1051 wR2 = 0.1195 wR2 = 0.0786 wR2 = 0.1638 wR2 = 0.0966
Final R indexes [all R1 = 0.1281, R1 = 0.1161, R1 = 0.0573, R1 = 0.1614, R1 = 0.1078,
data] wR2 = 0.1302 wR2 = 0.1418 wR2 = 0.0872 wR2 = 0.2074 wR2 = 0.1116
Largest diff.
0.68/-0.42 0.75/-1.26 0.51/-0.27 2.49/-1.14 0.62/-0.64
peak/hole / e Å-3
Table S3. Bond Lengths for 12a.

Atom Atom Length/Å Atom Atom Length/Å
Ru1 Cl1 2.3963(6) C16 C19 1.493(4)
Ru1 Cl2 2.4131(6) C21 C22 1.398(3)
Ru1 S1 2.3106(6) C21 C26 1.392(3)
Ru1 C2 2.019(2) C22 C23 1.393(3)
Ru1 C38 1.831(2) C22 C27 1.503(3)
S1 C31 1.806(2) C23 C24 1.379(4)
S1 C41 1.809(3) C24 C25 1.378(4)
N1 C2 1.349(3) C24 C28 1.525(4)
N1 C5 1.475(3) C25 C26 1.396(3)
S-36
N1 C11 1.438(3) C26 C29 1.500(3)
N3 C2 1.343(3) C31 C32 1.501(3)
N3 C4 1.476(3) C32 C33 1.388(3)
N3 C21 1.439(3) C32 C37 1.403(3)
C4 C5 1.514(3) C33 C34 1.371(4)
C11 C12 1.388(4) C34 C35 1.364(4)
C11 C16 1.400(4) C35 C36 1.382(4)
C12 C13 1.395(4) C36 C37 1.406(3)
C12 C17 1.497(4) C37 C38 1.458(3)
C13 C14 1.372(4) C41 C42 1.530(4)
C14 C15 1.371(4) C42 C43 1.463(4)
C14 C18 1.519(4) C43 C44 1.477(5)
C15 C16 1.395(4)
Table S4. Bond Angles for 12a.

Atom Atom Atom Angle/˚ Atom Atom Atom Angle/˚
Cl1 Ru1 Cl2 89.47(3) C14 C15 C16 122.4(3)
S1 Ru1 Cl1 91.47(2) C11 C16 C19 122.7(2)
S1 Ru1 Cl2 178.67(2) C15 C16 C11 117.3(3)
C2 Ru1 Cl1 158.00(6) C15 C16 C19 120.0(3)
C2 Ru1 Cl2 86.54(6) C22 C21 N3 118.2(2)
C2 Ru1 S1 92.23(6) C26 C21 N3 120.8(2)
C38 Ru1 Cl1 102.96(7) C26 C21 C22 120.9(2)
C38 Ru1 Cl2 90.09(8) C21 C22 C27 122.2(2)
C38 Ru1 S1 90.61(8) C23 C22 C21 118.2(2)
C38 Ru1 C2 98.68(9) C23 C22 C27 119.5(2)
C31 S1 Ru1 104.30(9) C24 C23 C22 122.1(2)
C31 S1 C41 97.90(12) C23 C24 C28 121.3(3)
C41 S1 Ru1 110.64(9) C25 C24 C23 118.3(2)
C2 N1 C5 112.35(18) C25 C24 C28 120.4(3)
C2 N1 C11 126.92(18) C24 C25 C26 122.0(3)
S-37
C11 N1 C5 119.27(18) C21 C26 C25 118.3(2)
C2 N3 C4 113.31(17) C21 C26 C29 123.1(2)
C2 N3 C21 125.64(18) C25 C26 C29 118.7(2)
113.88(1
C21 N3 C4 120.89(17) C32 C31 S1
7)
N1 C2 Ru1 132.00(15) C33 C32 C31 117.6(2)
N3 C2 Ru1 119.93(15) C33 C32 C37 119.2(2)
N3 C2 N1 107.54(18) C37 C32 C31 123.0(2)
N3 C4 C5 101.65(17) C34 C33 C32 122.2(3)
N1 C5 C4 102.95(18) C35 C34 C33 119.3(3)
C12 C11 N1 119.3(2) C34 C35 C36 120.4(3)
C12 C11 C16 121.9(2) C35 C36 C37 121.3(3)
C16 C11 N1 118.7(2) C32 C37 C36 117.7(2)
C11 C12 C13 117.3(3) C32 C37 C38 126.0(2)
C11 C12 C17 122.7(2) C36 C37 C38 116.3(2)
C13 C12 C17 119.9(3) C37 C38 Ru1 134.13(2)
C14 C13 C12 122.6(3) C42 C41 S1 111.3(2)
C13 C14 C18 120.8(3) C43 C42 C41 114.5(3)
C15 C14 C13 118.3(3) C42 C43 C44 116.0(3)
C15 C14 C18 120.9(3)
S-38
Figure S19. Asymmetric fragment of compound 12a.
Table S5. Bond Lengths for 12b.
Ru1 Cl1 2.4066(18) Ru2 C2A 2.018(7)
Ru1 Cl2 2.4066(18) Ru2 C38A 1.832(7)
Ru1 S1 2.3293(18) S1A C37A 1.822(7)
Ru1 C2 2.023(6) S1A C41A 1.828(8)

Ru1 C38 1.841(7) N1A C2A 1.347(8)
S1 C37 1.814(7) N1A C5A 1.471(8)
S1 C41 1.823(7) N1A C21A 1.450(8)
N1 C2 1.344(9) N3A C2A 1.331(9)
N1 C5 1.485(8) N3A C4A 1.473(8)
N1 C21 1.434(9) N3A C11A 1.463(8)
N3 C2 1.353(8) C4A C5A 1.532(10)
N3 C4 1.477(9) C11A C12A 1.377(9)
N3 C11 1.415(9) C11A C16A 1.411(10)
C4 C5 1.548(10) C12A C13A 1.398(10)
S-39
C11 C12 1.410(9) C12A C17A 1.494(10)
C11 C16 1.391(10) C13A C14A 1.399(10)
C12 C13 1.399(11) C14A C15A 1.386(10)
C12 C17 1.476(11) C14A C18A 1.530(10)
C13 C14 1.387(12) C15A C16A 1.371(10)
C14 C15 1.403(11) C16A C19A 1.499(10)
C14 C18 1.495(11) C21A C22A 1.389(10)
C15 C16 1.389(10) C21A C26A 1.418(10)
C16 C19 1.511(10) C22A C23A 1.393(10)
C21 C22 1.403(10) C22A C27A 1.506(10)
C21 C26 1.415(10) C23A C24A 1.370(11)
C22 C23 1.368(10) C24A C25A 1.382(12)
C22 C27 1.512(10) C24A C28A 1.522(11)
C23 C24 1.419(11) C25A C26A 1.396(10)
C24 C25 1.362(11) C26A C29A 1.486(11)
C24 C28 1.533(11) C31A C32A 1.401(10)
C25 C26 1.383(10) C31A C36A 1.419(10)
C26 C29 1.499(11) C31A C38A 1.451(9)
C31 C32 1.391(9) C32A C33A 1.412(10)
C31 C36 1.398(10) C32A C37A 1.490(11)
C31 C38 1.439(9) C33A C34A 1.382(11)
C32 C33 1.378(10) C34A C35A 1.372(12)
C33 C34 1.378(10) C35A C36A 1.371(10)
C34 C35 1.380(10) C41A C42A 1.527(11)
S-40
C35 C36 1.390(9) C42A C43A 1.496(13)
C36 C37 1.509(10) C42A C44A 1.531(12)
C41 C42 1.522(10) Cl3 C6 1.672(12)
C42 C43 1.522(10) Cl4 C6 1.675(12)
C42 C44 1.534(11) Cl5 C7 1.660(13)
Ru2 S1A 2.324(2) Cl6 C7 1.671(13)
Ru2 Cl1A 2.387(2) Cl7 C8 1.709(12)
Ru2 Cl2A 2.405(2) Cl8 C8 1.693(12)
Table S6. Bond Angles for 12b.

Cl2 Ru1 Cl1 89.40(6) Cl1A Ru2 Cl2A 88.13(7)
S1 Ru1 Cl1 91.19(6) C2A Ru2 S1A 93.3(2)
S1 Ru1 Cl2 179.41(6) C2A Ru2 Cl1A 155.4(2)
C2 Ru1 Cl1 158.0(2) C2A Ru2 Cl2A 86.4(2)
C2 Ru1 Cl2 85.20(18) C38A Ru2 S1A 90.3(2)
C2 Ru1 S1 94.26(18) C38A Ru2 Cl1A 106.5(2)
C38 Ru1 Cl1 103.9(2) C38A Ru2 Cl2A 91.3(2)
C38 Ru1 Cl2 88.2(2) C38A Ru2 C2A 97.6(3)
C38 Ru1 S1 91.6(2) C37A S1A Ru2 101.2(3)
C38 Ru1 C2 97.3(3) C37A S1A C41A 100.1(4)
C37 S1 Ru1 104.3(2) C41A S1A Ru2 109.2(3)
C37 S1 C41 97.5(3) C2A N1A C5A 113.1(6)
C41 S1 Ru1 109.9(2) C2A N1A C21A 126.8(6)
C2 N1 C5 112.7(6) C21A N1A C5A 119.4(5)
C2 N1 C21 125.6(6) C2A N3A C4A 112.7(5)
C21 N1 C5 121.5(6) C2A N3A C11A 128.9(5)
C2 N3 C4 112.3(6) C11A N3A C4A 115.8(5)
C2 N3 C11 127.0(6) N1A C2A Ru2 119.0(5)
S-41
C11 N3 C4 119.0(5) N3A C2A Ru2 131.8(5)
N1 C2 Ru1 117.7(5) N3A C2A N1A 108.1(6)
N1 C2 N3 108.9(6) N3A C4A C5A 102.3(5)
N3 C2 Ru1 132.7(5) N1A C5A C4A 101.3(5)
N3 C4 C5 102.6(5) C12A C11A N3A 117.9(6)
N1 C5 C4 101.7(5) C12A C11A C16A 122.9(6)
C12 C11 N3 119.3(6) C16A C11A N3A 118.8(6)
C16 C11 N3 120.0(6) C11A C12A C13A 117.6(7)
C16 C11 C12 120.7(7) C11A C12A C17A 123.4(6)
C11 C12 C17 121.9(7) C13A C12A C17A 119.0(6)
C13 C12 C11 118.0(7) C12A C13A C14A 121.3(6)
C13 C12 C17 120.1(7) C13A C14A C18A 120.7(7)
C14 C13 C12 122.3(7) C15A C14A C13A 118.3(6)
C13 C14 C15 118.1(7) C15A C14A C18A 120.9(7)
C13 C14 C18 121.5(8) C16A C15A C14A 122.8(7)
C15 C14 C18 120.3(9) C11A C16A C19A 122.5(6)
C16 C15 C14 121.2(7) C15A C16A C11A 117.0(6)
C11 C16 C19 121.9(6) C15A C16A C19A 120.5(7)
C15 C16 C11 119.6(7) C22A C21A N1A 121.0(6)
C15 C16 C19 118.4(7) C22A C21A C26A 121.6(6)
C22 C21 N1 118.1(6) C26A C21A N1A 116.9(6)
C22 C21 C26 121.9(7) C21A C22A C23A 117.3(7)
C26 C21 N1 119.9(7) C21A C22A C27A 123.4(6)
C21 C22 C27 121.0(7) C23A C22A C27A 119.3(7)
C23 C22 C21 118.7(7) C24A C23A C22A 123.5(8)
C23 C22 C27 120.3(7) C23A C24A C25A 117.9(7)
C22 C23 C24 120.8(7) C23A C24A C28A 122.2(8)
C23 C24 C28 119.0(8) C25A C24A C28A 119.9(8)
C25 C24 C23 118.3(7) C24A C25A C26A 122.5(7)
C25 C24 C28 122.7(8) C21A C26A C29A 121.8(7)
C24 C25 C26 124.0(7) C25A C26A C21A 117.2(7)
S-42
C21 C26 C29 122.9(7) C25A C26A C29A 120.9(7)
C25 C26 C21 116.0(7) C32A C31A C36A 118.4(7)
C25 C26 C29 121.1(7) C32A C31A C38A 123.9(7)
C32 C31 C36 117.8(6) C36A C31A C38A 117.7(7)
C32 C31 C38 116.9(6) C31A C32A C33A 118.5(7)
C36 C31 C38 125.3(6) C31A C32A C37A 122.2(7)
C33 C32 C31 122.5(7) C33A C32A C37A 119.2(7)
C32 C33 C34 118.7(7) C34A C33A C32A 121.5(8)
C33 C34 C35 120.7(7) C35A C34A C33A 119.7(8)
C34 C35 C36 120.2(7) C36A C35A C34A 120.5(8)
C31 C36 C37 123.9(6) C35A C36A C31A 121.2(7)
C35 C36 C31 120.1(6) C32A C37A S1A 110.4(5)
C35 C36 C37 115.8(6) C31A C38A Ru2 135.1(5)
C36 C37 S1 115.6(5) C42A C41A S1A 114.6(6)
C31 C38 Ru1 135.5(5) C41A C42A C44A 107.3(8)
C42 C41 S1 114.3(5) C43A C42A C41A 113.4(7)
C41 C42 C43 113.3(6) C43A C42A C44A 111.2(8)
C41 C42 C44 107.7(7) Cl3 C6 Cl4 115.2(10)
C43 C42 C44 109.9(7) Cl5 C7 Cl6 112.6(12)
S1A Ru2 Cl1A 91.52(8) Cl8 C8 Cl7 112.7(10)
S1A Ru2 Cl2A 178.42(7)
S-43
Figure S20. Asymmetric fragment of compound 12b. Atomic labels have been omitted for clarity.
Table S7. Bond Lengths for 11d.

Ru1 Cl2 2.3580(11) C5' C4A 1.400(6)
Ru1 Cl1 2.3625(12) C18 C15 1.498(6)
Ru1 S3 2.4058(11) C6 C7 1.374(7)
Ru1 C2 2.056(4) C13 C12 1.381(7)
Ru1 C1 1.833(4) C13 C14 1.382(7)
S3 C9 1.866(5) C8A C8 1.404(6)
S3 C4' 1.791(5) C8A C4A 1.399(6)
N1 C5 1.476(5) C8A C1 1.452(6)
N1 C2 1.347(5) C10 C15 1.399(6)
N1 C10 1.437(5) C10 C11 1.401(6)
N3 C19 1.425(5) C12 C11 1.381(6)
N3 C2 1.342(5) C14 C15 1.388(6)
N3 C4 1.476(5) C8 C7 1.379(6)
C22 C26 1.505(6) C4A C4' 1.510(6)
C22 C21 1.388(6) C31 C32 1.3900
C22 C23 1.389(6) C31 C36 1.3900
S-44
C24 C19 1.395(6) C31 C37 1.519(17)
C24 C23 1.387(6) C32 C33 1.3900
C24 C27 1.515(6) C33 C34 1.3900
C20 C21 1.394(6) C34 C35 1.3900
C20 C19 1.387(6) C35 C36 1.3900
C20 C25 1.502(6) C31B C32B 1.386(17)
C17 C13 1.510(6) C31B C36B 1.400(17)
C16 C11 1.501(6) C31B C37B 1.53(2)
C9 C28 1.529(7) C32B C33B 1.435(17)
C9 C30 1.508(7) C33B C34B 1.392(17)
C9 C29 1.506(8) C34B C35B 1.350(17)
C5 C4 1.515(6) C35B C36B 1.392(17)
C5' C6 1.366(7)
Two crystallographically independent molecules of the complex in 12b have the same
conformation, the mean-square deviation of atoms when the molecules are superimposed on each
other (Fig. 2) is 0.26 Å.
Figure S21. Superposition of two crystallographically independent molecules of the complex in

12b.
Table S8. Bond Angles for 3.
Cl2 Ru1 Cl1 167.75(5) C4A C8A C1 126.6(4)
Cl2 Ru1 S3 93.37(4) C24 C19 N3 119.3(4)
Cl1 Ru1 S3 83.39(4) C20 C19 N3 119.2(4)
S-45
C2 Ru1 Cl2 88.20(11) C20 C19 C24 121.5(4)
C2 Ru1 Cl1 93.42(11) N1 C2 Ru1 119.9(3)
C2 Ru1 S3 171.90(12) N3 C2 Ru1 132.7(3)
C1 Ru1 Cl2 93.52(13) N3 C2 N1 107.0(3)
C1 Ru1 Cl1 98.10(13) C15 C10 N1 120.0(4)
C1 Ru1 S3 87.23(13) C15 C10 C11 121.2(4)
C1 Ru1 C2 100.62(17) C11 C10 N1 118.7(4)
C9 S3 Ru1 112.60(16) C13 C12 C11 122.4(4)
C4' S3 Ru1 102.30(15) C24 C23 C22 121.5(4)
C4' S3 C9 104.0(2) C13 C14 C15 122.3(4)
C2 N1 C5 114.2(3) C10 C15 C18 122.7(4)
C2 N1 C10 124.9(3) C14 C15 C18 119.6(4)
C10 N1 C5 120.8(3) C14 C15 C10 117.7(4)
C19 N3 C4 118.7(3) C7 C8 C8A 122.3(4)
C2 N3 C19 126.7(3) C5' C4A C4' 117.3(4)
C2 N3 C4 113.5(3) C8A C4A C5' 118.8(4)
C21 C22 C26 120.9(4) C8A C4A C4' 123.8(4)
C21 C22 C23 118.2(4) C10 C11 C16 122.2(4)
C23 C22 C26 120.8(4) C12 C11 C16 119.8(4)
C19 C24 C27 121.0(4) C12 C11 C10 118.0(4)
C23 C24 C19 118.6(4) C8A C1 Ru1 133.5(3)
C23 C24 C27 120.3(4) C6 C7 C8 118.6(4)
C21 C20 C25 120.9(4) C4A C4' S3 108.9(3)
C19 C20 C21 118.1(4) N3 C4 C5 103.2(3)
C19 C20 C25 121.0(4) C32 C31 C36 120.0
C28 C9 S3 106.8(3) C32 C31 C37 120.2(8)
S-46
C30 C9 S3 103.8(4) C36 C31 C37 119.4(8)
C30 C9 C28 110.5(4) C33 C32 C31 120.0
C29 C9 S3 113.1(4) C32 C33 C34 120.0
C29 C9 C28 110.0(5) C35 C34 C33 120.0
C29 C9 C30 112.4(5) C36 C35 C34 120.0
N1 C5 C4 102.1(3) C35 C36 C31 120.0
C6 C5' C4A 121.3(4) C32B C31B C36B 118.4(17)
C5' C6 C7 120.8(4) C32B C31B C37B 125(2)
C12 C13 C17 121.9(4) C36B C31B C37B 116(2)
C12 C13 C14 118.1(4) C31B C32B C33B 122.5(19)
C14 C13 C17 120.0(4) C34B C33B C32B 117.8(19)
C22 C21 C20 122.0(4) C35B C34B C33B 117.4(19)
C8 C8A C1 115.4(4) C34B C35B C36B 127(2)
C4A C8A C8 118.0(4) C35B C36B C31B 116.6(18)
S-47
Figure S22. Asymmetric fragment of compound 11d. Only one position of disordered toluene is
shown.
Table S9. Bond Lengths for 12f.
Ru1 Cl1 2.4120(10) C16 C19 1.503(6)
Ru1 Cl2 2.3941(11) C21 C22 1.391(5)
Ru1 S1 2.3091(10) C21 C26 1.394(5)
Ru1 C2 2.036(3) C22 C23 1.390(5)
Ru1 C38 1.835(4) C22 C27 1.507(5)
Cl3 C6 1.730(6) C23 C24 1.386(6)
Cl4 C6 1.719(6) C24 C25 1.362(6)
S1 C31 1.823(4) C24 C28 1.523(6)
S1 C41 1.793(4) C25 C26 1.401(6)
N1 C2 1.341(4) C26 C29 1.499(6)
N1 C5 1.478(5) C31 C32 1.500(6)
N1 C11 1.433(4) C32 C33 1.399(5)
N3 C2 1.341(4) C32 C37 1.387(6)
N3 C4 1.477(4) C33 C34 1.366(7)
N3 C21 1.436(5) C34 C35 1.356(7)
C4 C5 1.508(5) C35 C36 1.384(6)
C11 C12 1.395(6) C36 C37 1.404(5)
C11 C16 1.388(6) C37 C38 1.467(5)
C12 C13 1.400(6) C41 C42 1.377(6)
C12 C17 1.506(6) C41 C46 1.372(6)
C13 C14 1.372(7) C42 C43 1.381(7)
C14 C15 1.371(6) C43 C44 1.365(8)
C14 C18 1.520(6) C44 C45 1.350(8)
C15 C16 1.405(6) C45 C46 1.380(7)
Table S10. Bond Angles for 12f.

Cl2 Ru1 Cl1 86.77(4) C11 C16 C19 122.9(4)
S-48
S1 Ru1 Cl1 93.13(4) C15 C16 C19 119.7(4)
S1 Ru1 Cl2 179.56(4) C22 C21 N3 118.7(3)
C2 Ru1 Cl1 162.94(10) C22 C21 C26 121.7(4)
C2 Ru1 Cl2 87.69(10) C26 C21 N3 119.5(3)
C2 Ru1 S1 92.28(10) C21 C22 C27 122.1(4)
C38 Ru1 Cl1 98.25(11) C23 C22 C21 118.4(4)
C38 Ru1 Cl2 91.69(13) C23 C22 C27 119.5(4)
C38 Ru1 S1 88.75(12) C24 C23 C22 121.4(4)
C38 Ru1 C2 98.03(14) C23 C24 C28 121.0(5)
C31 S1 Ru1 103.41(16) C25 C24 C23 118.7(4)
C41 S1 Ru1 116.48(14) C25 C24 C28 120.3(5)
C41 S1 C31 97.96(19) C24 C25 C26 122.7(4)
C2 N1 C5 112.9(3) C21 C26 C25 117.1(4)
C2 N1 C11 128.2(3) C21 C26 C29 122.9(4)
C11 N1 C5 118.3(3) C25 C26 C29 119.9(4)
C2 N3 C4 113.2(3) C32 C31 S1 111.0(3)
C2 N3 C21 126.2(3) C33 C32 C31 117.0(4)
C21 N3 C4 120.5(3) C37 C32 C31 123.9(4)
N1 C2 Ru1 131.3(2) C37 C32 C33 119.0(4)
N1 C2 N3 107.6(3) C34 C33 C32 121.4(5)
N3 C2 Ru1 120.7(2) C35 C34 C33 119.9(5)
N3 C4 C5 102.3(3) C34 C35 C36 120.7(5)
N1 C5 C4 102.8(3) C35 C36 C37 120.1(5)
Cl4 C6 Cl3 111.4(3) C32 C37 C36 119.0(4)
C12 C11 N1 119.3(4) C32 C37 C38 125.3(4)
C16 C11 N1 118.4(4) C36 C37 C38 115.8(4)
C16 C11 C12 122.2(4) C37 C38 Ru1 134.2(3)
C11 C12 C13 117.0(4) C42 C41 S1 116.1(4)
C11 C12 C17 122.4(4) C46 C41 S1 122.9(3)
C13 C12 C17 120.6(4) C46 C41 C42 121.0(4)
C14 C13 C12 122.7(5) C41 C42 C43 119.3(5)
S-49
C13 C14 C18 120.7(5) C44 C43 C42 119.6(5)
C15 C14 C13 118.4(4) C45 C44 C43 120.6(5)
C15 C14 C18 120.8(5) C44 C45 C46 121.2(5)
C14 C15 C16 122.1(5) C41 C46 C45 118.2(5)
C11 C16 C15 117.4(4)
Figure S23. Asymmetric fragment of compound 12f.

Table S11. Bond Lengths for 12g.
Ru1 Cl1 2.3909(8) C16 C19 1.502(5)
Ru1 Cl2 2.4065(8) C21 C22 1.402(4)
Ru1 S1 2.3053(7) C21 C26 1.392(4)
Ru1 C2 2.021(2) C22 C23 1.382(4)
Ru1 C38 1.837(3) C22 C27 1.511(4)
S1 C31 1.809(3) C23 C24 1.378(5)
S1 C41 1.787(3) C24 C25 1.379(5)
O1 N2 1.226(4) C24 C28 1.518(4)
S-50
O2 N2 1.214(4) C25 C26 1.398(4)
N1 C2 1.338(3) C26 C29 1.506(4)
N1 C5 1.479(3) C31 C32 1.497(4)
N1 C11 1.443(3) C32 C33 1.391(4)
N2 C44 1.478(4) C32 C37 1.409(4)
N3 C2 1.349(3) C33 C34 1.372(4)
N3 C4 1.473(3) C34 C35 1.370(4)
N3 C21 1.441(3) C35 C36 1.381(4)
C4 C5 1.505(4) C36 C37 1.404(4)
C11 C12 1.394(4) C37 C38 1.456(3)
C11 C16 1.398(4) C41 C42 1.387(4)
C12 C13 1.391(4) C41 C46 1.381(4)
C12 C17 1.498(4) C42 C43 1.374(4)
C13 C14 1.378(5) C43 C44 1.376(5)
C14 C15 1.376(5) C44 C45 1.364(5)
C14 C18 1.514(4) C45 C46 1.376(4)
C15 C16 1.390(4)
Table S12. Bond Angles for 12g.

Cl1 Ru1 Cl2 89.18(4) C15 C16 C11 117.6(3)
S1 Ru1 Cl1 94.68(3) C15 C16 C19 119.7(3)
S1 Ru1 Cl2 176.04(3) C22 C21 N3 118.3(2)
C2 Ru1 Cl1 159.27(7) C26 C21 N3 121.0(2)
C2 Ru1 Cl2 86.41(7) C26 C21 C22 120.5(3)
C2 Ru1 S1 90.28(7) C21 C22 C27 121.6(3)
C38 Ru1 Cl1 101.94(8) C23 C22 C21 118.6(3)
C38 Ru1 Cl2 89.09(9) C23 C22 C27 119.8(3)
C38 Ru1 S1 89.25(9) C24 C23 C22 122.6(3)
C38 Ru1 C2 98.23(11) C23 C24 C25 117.7(3)
C31 S1 Ru1 104.28(12) C23 C24 C28 121.3(3)
S-51
C41 S1 Ru1 118.61(10) C25 C24 C28 121.0(4)
C41 S1 C31 97.92(13) C24 C25 C26 122.4(3)
C2 N1 C5 112.3(2) C21 C26 C25 118.1(3)
C2 N1 C11 127.6(2) C21 C26 C29 122.6(3)
C11 N1 C5 118.7(2) C25 C26 C29 119.2(3)
O1 N2 C44 117.2(3) C32 C31 S1 111.8(2)
O2 N2 O1 124.8(3) C33 C32 C31 118.3(3)
O2 N2 C44 118.0(4) C33 C32 C37 119.0(3)
C2 N3 C4 112.6(2) C37 C32 C31 122.5(2)
C2 N3 C21 127.0(2) C34 C33 C32 121.6(3)
C21 N3 C4 120.2(2) C35 C34 C33 120.1(3)
N1 C2 Ru1 131.39(18) C34 C35 C36 119.8(3)
N1 C2 N3 108.0(2) C35 C36 C37 121.4(3)
N3 C2 Ru1 120.22(19) C32 C37 C38 125.3(2)
N3 C4 C5 102.3(2) C36 C37 C32 118.0(2)
N1 C5 C4 102.8(2) C36 C37 C38 116.7(3)
C12 C11 N1 119.2(2) C37 C38 Ru1 135.1(2)
C12 C11 C16 121.5(3) C42 C41 S1 115.7(2)
C16 C11 N1 119.1(2) C46 C41 S1 123.8(2)
C11 C12 C17 122.5(3) C46 C41 C42 120.4(3)
C13 C12 C11 117.8(3) C43 C42 C41 120.3(3)
C13 C12 C17 119.7(3) C42 C43 C44 118.0(3)
C14 C13 C12 122.5(3) C43 C44 N2 118.4(3)
C13 C14 C18 121.3(3) C45 C44 N2 118.8(3)
C15 C14 C13 118.0(3) C45 C44 C43 122.8(3)
C15 C14 C18 120.7(3) C44 C45 C46 119.1(3)
C14 C15 C16 122.7(3) C45 C46 C41 119.5(3)
C11 C16 C19 122.7(3)
S-52
Figure S24. Asymmetric fragment of compound 12g.
Table S13. Bond Lengths for 12g.
Ru1 Cl1 2.3297(12) C22 C23 1.385(8)
Ru1 Cl2 2.3443(11) C22 C27 1.506(7)
Ru1 S1 2.4078(12) C23 C24 1.389(8)
Ru1 C2 2.061(5) C24 C25 1.372(8)
Ru1 C38 1.838(5) C24 C28 1.538(9)
S1 C31 1.798(5) C25 C26 1.391(7)
S1 C41 1.807(5) C26 C29 1.502(7)
N1 C2 1.337(6) C31 C32 1.521(7)
N1 C5 1.478(6) C32 C33 1.373(7)
N1 C11 1.415(6) C32 C37 1.397(6)
N3 C2 1.356(6) C33 C34 1.381(8)
N3 C4 1.474(6) C34 C35 1.385(7)
N3 C21 1.420(6) C35 C36 1.354(7)
C4 C5 1.501(7) C36 C37 1.392(6)
C11 C12 1.382(7) C37 C38 1.460(6)
C11 C16 1.391(7) C41 C42 1.364(7)
S-53
C12 C13 1.399(7) C41 C46 1.359(7)
C12 C17 1.509(7) C42 C43 1.347(8)
C13 C14 1.389(8) C43 C44 1.327(9)
C14 C15 1.360(8) C44 C45 1.365(9)
C14 C18 1.523(8) C44 N2 1.499(10)
C15 C16 1.376(8) C45 C46 1.378(8)
C16 C19 1.498(8) N2 O1 1.176(9)
C21 C22 1.390(7) N2 O2 1.215(9)
C21 C26 1.402(7)
Table S14. Bond Angles for 11g.

Cl1 Ru1 Cl2 164.50(6) C22 C21 C26 120.8(5)
Cl1 Ru1 S1 90.21(5) C26 C21 N3 118.9(5)
Cl2 Ru1 S1 85.58(4) C21 C22 C27 121.7(6)
C2 Ru1 Cl1 88.86(12) C23 C22 C21 118.8(5)
C2 Ru1 Cl2 93.77(12) C23 C22 C27 119.4(6)
C2 Ru1 S1 174.04(15) C22 C23 C24 121.6(6)
C38 Ru1 Cl1 97.62(15) C23 C24 C28 120.8(8)
C38 Ru1 Cl2 96.96(15) C25 C24 C23 118.3(6)
C38 Ru1 S1 85.94(15) C25 C24 C28 120.8(7)
C38 Ru1 C2 100.0(2) C24 C25 C26 122.5(6)
C31 S1 Ru1 103.83(19) C21 C26 C29 121.5(5)
C31 S1 C41 99.2(3) C25 C26 C21 117.7(5)
C41 S1 Ru1 106.96(17) C25 C26 C29 120.5(5)
C2 N1 C5 112.9(4) C32 C31 S1 110.8(4)
C2 N1 C11 127.9(4) C33 C32 C31 115.1(5)
C11 N1 C5 119.2(4) C33 C32 C37 119.8(5)
C2 N3 C4 113.0(4) C37 C32 C31 125.1(4)
C2 N3 C21 127.5(4) C32 C33 C34 122.2(5)
C21 N3 C4 119.1(4) C33 C34 C35 117.7(5)
S-54
N1 C2 Ru1 132.1(4) C36 C35 C34 120.6(6)
N1 C2 N3 107.7(4) C35 C36 C37 122.3(5)
N3 C2 Ru1 119.9(4) C32 C37 C38 125.8(5)
N3 C4 C5 102.8(4) C36 C37 C32 117.3(4)
N1 C5 C4 103.6(4) C36 C37 C38 117.0(4)
C12 C11 N1 119.1(5) C37 C38 Ru1 135.0(4)
C12 C11 C16 122.1(5) C42 C41 S1 122.7(4)
C16 C11 N1 118.8(5) C46 C41 S1 118.4(4)
C11 C12 C13 117.6(5) C46 C41 C42 118.7(5)
C11 C12 C17 122.0(5) C43 C42 C41 121.2(6)
C13 C12 C17 120.4(6) C44 C43 C42 119.5(6)
C14 C13 C12 121.4(6) C43 C44 C45 122.1(6)
C13 C14 C18 119.5(7) C43 C44 N2 118.8(7)
C15 C14 C13 118.1(6) C45 C44 N2 119.1(8)
C15 C14 C18 122.3(7) C44 C45 C46 117.7(6)
C14 C15 C16 123.3(6) C41 C46 C45 120.6(6)
C11 C16 C19 121.3(6) O1 N2 C44 118.8(9)
C15 C16 C11 117.4(6) O1 N2 O2 123.8(9)
C15 C16 C19 121.3(6) O2 N2 C44 117.0(9)
C22 C21 N3 120.1(5)
S-55
Figure S25. Asymmetric fragment of compound 11g.
Table S15. Bond Lengths for 12e.

Ru1 Cl1 2.408(3) S1A C41A 1.780(13)
Ru1 Cl2 2.391(4) O1A C44A 1.389(15)
Ru1 S1 2.319(3) O1A C47A 1.430(16)
Ru1 C2 2.058(12) N1A C2A 1.346(16)
Ru1 C38 1.847(12) N1A C5A 1.506(16)
S1 C31 1.820(14) N1A C11A 1.442(15)
S1 C41 1.813(12) N3A C2A 1.339(15)
O1 C44 1.375(15) N3A C4A 1.474(14)
O1 C47 1.453(15) N3A C21A 1.443(15)
N1 C2 1.335(15) C4A C5A 1.481(16)
N1 C5 1.472(16) C11A C12A 1.381(19)
N1 C11 1.419(15) C11A C16A 1.423(18)
N3 C2 1.354(15) C12A C13A 1.385(18)
N3 C4 1.476(16) C12A C17A 1.522(17)
N3 C21 1.423(16) C13A C14A 1.346(19)
S-56
C4 C5 1.535(18) C14A C15A 1.419(19)
C11 C12 1.412(18) C14A C18A 1.512(18)
C11 C16 1.384(18) C15A C16A 1.424(18)
C12 C13 1.398(17) C16A C19A 1.491(18)
C12 C17 1.501(18) C21A C22A 1.385(17)
C13 C14 1.415(19) C21A C26A 1.417(19)
C14 C15 1.371(19) C22A C23A 1.394(17)
C14 C18 1.517(19) C22A C27A 1.526(18)
C15 C16 1.381(18) C23A C24A 1.355(19)
C16 C19 1.524(18) C24A C25A 1.395(19)
C21 C22 1.408(18) C24A C28A 1.532(18)
C21 C26 1.405(18) C25A C26A 1.387(17)
C22 C23 1.383(18) C26A C29A 1.500(17)
C22 C27 1.505(18) C31A C32A 1.526(17)
C23 C24 1.408(19) C32A C33A 1.432(17)
C24 C25 1.392(19) C32A C37A 1.417(18)
C24 C28 1.502(17) C33A C34A 1.383(17)
C25 C26 1.386(18) C34A C35A 1.353(19)
C26 C29 1.524(19) C35A C36A 1.373(18)
C31 C32 1.479(17) C36A C37A 1.385(17)
C32 C33 1.349(17) C37A C38A 1.458(17)
C32 C37 1.416(17) C41A C42A 1.368(18)
C33 C34 1.414(18) C41A C46A 1.379(18)
C34 C35 1.406(17) C42A C43A 1.366(17)
C35 C36 1.383(17) C43A C44A 1.421(19)
C36 C37 1.412(17) C44A C45A 1.376(19)
C37 C38 1.465(16) C45A C46A 1.386(18)
C41 C42 1.401(16) Cl3 C51 1.78(2)
C41 C46 1.407(16) Cl4 C51 1.800(18)
C42 C43 1.410(17) Cl5 C52 1.744(17)
C43 C44 1.350(18) Cl6 C52 1.804(17)
S-57
C44 C45 1.423(18) Cl7 C53 1.758(14)
C45 C46 1.380(16) Cl8 C53 1.725(13)
Ru1A Cl1A 2.426(3) Cl9 C54 1.735(14)
Ru1A Cl2A 2.386(3) Cl10 C54 1.761(15)
Ru1A S1A 2.323(4) Cl11 C55 1.690(16)
Ru1A C2A 2.033(14) Cl12 C55 1.753(17)
Ru1A C38A 1.826(13) Cl13 C56 1.769(14)
S1A C31A 1.819(12) Cl14 C56 1.798(16)
Table S16. Bond Angles for 12e.

Cl2 Ru1 Cl1 86.80(12) C2A Ru1A Cl1A 160.3(4)
S1 Ru1 Cl1 90.23(12) C2A Ru1A Cl2A 88.3(4)
S1 Ru1 Cl2 176.99(13) C2A Ru1A S1A 94.7(4)
C2 Ru1 Cl1 163.5(4) C38A Ru1A Cl1A 104.5(4)
C2 Ru1 Cl2 90.4(4) C38A Ru1A Cl2A 90.5(4)
C2 Ru1 S1 92.3(4) C38A Ru1A S1A 89.4(5)
C38 Ru1 Cl1 101.6(4) C38A Ru1A C2A 94.6(5)
C38 Ru1 Cl2 90.8(4) C31A S1A Ru1A 102.2(4)
C38 Ru1 S1 90.2(4) C41A S1A Ru1A 114.4(5)
C38 Ru1 C2 94.7(5) C41A S1A C31A 99.1(6)
C31 S1 Ru1 102.2(5) C44A O1A C47A 116.4(11)
C41 S1 Ru1 113.9(4) C2A N1A C5A 112.4(11)
C41 S1 C31 100.1(6) C2A N1A C11A 132.8(12)
C44 O1 C47 116.5(11) C11A N1A C5A 114.7(10)
C2 N1 C5 112.6(11) C2A N3A C4A 113.3(9)
C2 N1 C11 129.9(11) C2A N3A C21A 126.2(11)
C11 N1 C5 117.4(11) C21A N3A C4A 120.3(10)
C2 N3 C4 113.9(10) N1A C2A Ru1A 131.8(10)
C2 N3 C21 127.5(11) N3A C2A Ru1A 120.6(9)
C21 N3 C4 118.2(10) N3A C2A N1A 107.6(12)
S-58
N1 C2 Ru1 132.8(10) N3A C4A C5A 104.0(9)
N1 C2 N3 108.2(11) C4A C5A N1A 102.6(10)
N3 C2 Ru1 118.8(9) C12A C11A N1A 120.2(13)
N3 C4 C5 101.1(10) C12A C11A C16A 122.1(12)
N1 C5 C4 104.0(11) C16A C11A N1A 117.4(13)
C12 C11 N1 118.7(12) C11A C12A C13A 119.1(13)
C16 C11 N1 119.3(12) C11A C12A C17A 120.9(12)
C16 C11 C12 121.8(13) C13A C12A C17A 120.0(14)
C11 C12 C17 121.2(12) C14A C13A C12A 122.8(15)
C13 C12 C11 116.0(13) C13A C14A C15A 118.7(13)
C13 C12 C17 122.6(13) C13A C14A C18A 123.2(14)
C12 C13 C14 122.4(14) C15A C14A C18A 118.1(14)
C13 C14 C18 118.1(14) C14A C15A C16A 121.5(13)
C15 C14 C13 118.8(13) C11A C16A C15A 115.8(13)
C15 C14 C18 123.2(14) C11A C16A C19A 123.0(12)
C14 C15 C16 120.6(13) C15A C16A C19A 121.2(13)
C11 C16 C19 120.7(12) C22A C21A N3A 119.1(12)
C15 C16 C11 120.3(14) C22A C21A C26A 121.7(12)
C15 C16 C19 118.8(12) C26A C21A N3A 119.1(12)
C22 C21 N3 118.9(12) C21A C22A C23A 118.2(13)
C26 C21 N3 120.1(13) C21A C22A C27A 122.2(12)
C26 C21 C22 120.5(12) C23A C22A C27A 119.6(12)
C21 C22 C27 120.1(12) C24A C23A C22A 122.0(14)
C23 C22 C21 118.2(13) C23A C24A C25A 119.1(13)
C23 C22 C27 121.7(13) C23A C24A C28A 120.8(14)
C22 C23 C24 122.3(13) C25A C24A C28A 120.1(13)
C23 C24 C28 121.4(13) C26A C25A C24A 121.9(13)
C25 C24 C23 117.9(12) C21A C26A C29A 121.6(12)
C25 C24 C28 120.7(13) C25A C26A C21A 116.9(12)
C26 C25 C24 121.5(14) C25A C26A C29A 121.1(13)
C21 C26 C29 122.4(13) C32A C31A S1A 109.7(9)
S-59
C25 C26 C21 119.2(14) C33A C32A C31A 118.2(12)
C25 C26 C29 118.3(14) C37A C32A C31A 123.5(11)
C32 C31 S1 112.9(10) C37A C32A C33A 118.2(12)
C33 C32 C31 119.7(13) C34A C33A C32A 120.0(13)
C33 C32 C37 120.1(12) C35A C34A C33A 119.7(14)
C37 C32 C31 120.1(12) C34A C35A C36A 122.6(14)
C32 C33 C34 122.3(13) C35A C36A C37A 120.0(13)
C35 C34 C33 119.1(13) C32A C37A C38A 121.7(12)
C36 C35 C34 117.9(13) C36A C37A C32A 119.5(12)
C35 C36 C37 123.4(13) C36A C37A C38A 118.8(12)
C32 C37 C38 126.1(12) C37A C38A Ru1A 137.6(10)
C36 C37 C32 117.1(12) C42A C41A S1A 118.6(10)
C36 C37 C38 116.8(11) C42A C41A C46A 117.6(12)
C37 C38 Ru1 134.1(9) C46A C41A S1A 123.7(11)
C42 C41 S1 117.3(9) C43A C42A C41A 123.9(13)
C42 C41 C46 121.0(11) C42A C43A C44A 117.2(13)
C46 C41 S1 121.0(10) O1A C44A C43A 124.2(13)
C41 C42 C43 118.3(12) C45A C44A O1A 115.6(13)
C44 C43 C42 121.6(13) C45A C44A C43A 120.3(13)
O1 C44 C45 115.1(12) C44A C45A C46A 119.3(13)
C43 C44 O1 125.5(13) C41A C46A C45A 121.5(13)
C43 C44 C45 119.4(13) Cl3 C51 Cl4 111.0(9)
C46 C45 C44 120.9(13) Cl5 C52 Cl6 110.4(10)
C45 C46 C41 118.5(12) Cl8 C53 Cl7 111.1(8)
Cl2A Ru1A Cl1A 86.61(12) Cl9 C54 Cl10 112.3(7)
S1A Ru1A Cl1A 90.47(12) Cl11 C55 Cl12 117.1(9)
S1A Ru1A Cl2A 176.95(13) Cl13 C56 Cl14 110.0(8)
S-60
Figure S26. Asymmetric fragment of compound 12e. Atomic labels have been omitted for
clarity.
Table S17. Bond Lengths for 11e.
Ru1 Cl1 2.3335(7) C16 C19 1.494(5)
Ru1 Cl2 2.3520(6) C21 C22 1.387(4)
Ru1 S1 2.4087(6) C21 C26 1.392(4)
Ru1 C2 2.055(2) C22 C23 1.398(4)
Ru1 C38 1.834(2) C22 C27 1.514(4)
S1 C31 1.811(3) C23 C24 1.376(4)
S1 C41 1.785(3) C24 C25 1.362(4)
O1 C44 1.387(4) C24 C28 1.531(4)
O1 C47 1.327(7) C25 C26 1.374(4)
N1 C2 1.345(3) C26 C29 1.503(4)
N1 C5 1.475(3) C31 C32 1.508(4)
N1 C11 1.425(3) C32 C33 1.386(4)
N3 C2 1.344(3) C32 C37 1.404(3)
S-61
N3 C4 1.473(3) C33 C34 1.378(4)
N3 C21 1.438(3) C34 C35 1.371(4)
C4 C5 1.495(4) C35 C36 1.378(4)
C11 C12 1.376(5) C36 C37 1.402(3)
C11 C16 1.397(4) C37 C38 1.463(3)
C12 C13 1.395(4) C41 C42 1.350(4)
C12 C17 1.517(4) C41 C46 1.351(4)
C13 C14 1.374(5) C42 C43 1.375(5)
C14 C15 1.365(6) C43 C44 1.330(5)
C14 C18 1.534(5) C44 C45 1.355(5)
C15 C16 1.398(5) C45 C46 1.382(5)
Table S18. Bond Angles for 11e.

Cl1 Ru1 Cl2 163.52(3) C15 C16 C19 121.5(4)
Cl1 Ru1 S1 90.83(3) C22 C21 N3 119.4(2)
Cl2 Ru1 S1 85.61(2) C22 C21 C26 121.6(2)
C2 Ru1 Cl1 87.52(7) C26 C21 N3 118.5(2)
C2 Ru1 Cl2 94.10(7) C21 C22 C23 116.7(3)
C2 Ru1 S1 173.15(7) C21 C22 C27 123.1(3)
C38 Ru1 Cl1 98.45(8) C23 C22 C27 120.1(3)
C38 Ru1 Cl2 97.39(8) C24 C23 C22 122.0(3)
C38 Ru1 S1 86.50(8) C23 C24 C28 119.9(4)
C38 Ru1 C2 100.32(10) C25 C24 C23 119.0(3)
C31 S1 Ru1 102.35(11) C25 C24 C28 121.1(3)
C41 S1 Ru1 107.96(9) C24 C25 C26 121.7(3)
C41 S1 C31 100.05(13) C21 C26 C29 122.2(3)
C47 O1 C44 119.4(5) C25 C26 C21 118.4(3)
C2 N1 C5 113.4(2) C25 C26 C29 119.2(3)
C2 N1 C11 127.8(2) C32 C31 S1 110.13(19)
C11 N1 C5 118.7(2) C33 C32 C31 116.6(2)
S-62
C2 N3 C4 113.6(2) C33 C32 C37 119.3(2)
C2 N3 C21 126.5(2) C37 C32 C31 124.0(2)
C21 N3 C4 119.5(2) C34 C33 C32 121.5(3)
N1 C2 Ru1 132.23(18) C35 C34 C33 119.8(3)
N3 C2 Ru1 120.48(17) C34 C35 C36 119.9(3)
N3 C2 N1 106.8(2) C35 C36 C37 121.6(3)
N3 C4 C5 102.9(2) C32 C37 C38 126.4(2)
N1 C5 C4 103.1(2) C36 C37 C32 117.9(2)
C12 C11 N1 118.9(3) C36 C37 C38 115.6(2)
C12 C11 C16 122.7(3) C37 C38 Ru1 134.10(19)
C16 C11 N1 118.3(3) C42 C41 S1 122.2(2)
C11 C12 C13 117.6(3) C42 C41 C46 117.9(3)
C11 C12 C17 122.5(3) C46 C41 S1 119.7(2)
C13 C12 C17 119.9(3) C41 C42 C43 121.8(3)
C14 C13 C12 121.8(4) C44 C43 C42 120.0(3)
C13 C14 C18 120.8(4) C43 C44 O1 124.9(4)
C15 C14 C13 118.8(3) C43 C44 C45 119.5(3)
C15 C14 C18 120.4(4) C45 C44 O1 115.6(4)
C14 C15 C16 122.4(4) C44 C45 C46 120.3(4)
C11 C16 C15 116.6(4) C41 C46 C45 120.4(3)
C11 C16 C19 121.8(3)
S-63
Figure S27. Asymmetric fragment of compound 11e.
Table S19. Bond Lengths for 12h.
Ru1 Cl1 2.414(2) C22 C27 1.497(14)
Ru1 Cl2 2.3799(19) C23 C24 1.341(16)
Ru1 S1 2.3119(19) C24 C25 1.388(16)
Ru1 C2 2.054(7) C24 C28 1.508(16)
Ru1 C38 1.818(8) C25 C26 1.410(14)
S1 C31 1.818(8) C26 C29 1.496(13)
S1 C41 1.801(7) C31 C32 1.492(12)
N1 C2 1.337(10) C32 C33 1.395(12)
N1 C5 1.482(10) C32 C37 1.421(12)
N1 C21 1.435(11) C33 C34 1.353(14)
N3 C2 1.352(10) C34 C35 1.403(15)
N3 C4 1.466(10) C35 C36 1.356(13)
N3 C11 1.431(10) C36 C37 1.389(12)
C4 C5 1.497(13) C37 C38 1.456(11)
C11 C12 1.385(12) C41 C42 1.412(11)
S-64
C11 C16 1.415(12) C41 C46 1.366(11)
C12 C13 1.390(13) C42 C43 1.358(12)
C12 C17 1.510(13) C43 C44 1.397(12)
C13 C14 1.390(14) C44 C45 1.436(11)
C14 C15 1.358(14) C44 C47 1.441(13)
C14 C18 1.520(13) C45 C46 1.404(11)
C15 C16 1.398(13) C45 C50 1.407(13)
C16 C19 1.492(13) C47 C48 1.337(14)
C21 C22 1.404(12) C48 C49 1.396(14)
C21 C26 1.383(13) C49 C50 1.356(13)
C22 C23 1.389(14)
Table S20. Bond Angles for 12h.

Cl2 Ru1 Cl1 87.31(8) C26 C21 C22 121.9(9)
S1 Ru1 Cl1 92.04(7) C21 C22 C27 122.7(9)
S1 Ru1 Cl2 176.77(8) C23 C22 C21 116.5(10)
C2 Ru1 Cl1 163.5(2) C23 C22 C27 120.8(9)
C2 Ru1 Cl2 86.0(2) C24 C23 C22 124.5(11)
C2 Ru1 S1 93.8(2) C23 C24 C25 117.8(11)
C38 Ru1 Cl1 96.3(2) C23 C24 C28 123.4(13)
C38 Ru1 Cl2 94.1(3) C25 C24 C28 118.9(13)
C38 Ru1 S1 89.1(3) C24 C25 C26 121.9(11)
C38 Ru1 C2 99.1(3) C21 C26 C25 117.3(10)
C31 S1 Ru1 103.5(3) C21 C26 C29 121.9(9)
C41 S1 Ru1 112.4(3) C25 C26 C29 120.8(10)
C41 S1 C31 99.9(4) C32 C31 S1 111.2(6)
C2 N1 C5 112.1(7) C33 C32 C31 118.5(8)
C2 N1 C21 128.4(7) C33 C32 C37 117.7(9)
C21 N1 C5 118.7(7) C37 C32 C31 123.6(8)
C2 N3 C4 113.1(7) C34 C33 C32 122.5(10)
S-65
C2 N3 C11 128.9(6) C33 C34 C35 120.6(10)
C11 N3 C4 117.7(6) C36 C35 C34 117.2(10)
N1 C2 Ru1 130.9(6) C35 C36 C37 124.5(9)
N1 C2 N3 107.7(6) C32 C37 C38 124.1(8)
N3 C2 Ru1 120.4(6) C36 C37 C32 117.5(8)
N3 C4 C5 102.4(7) C36 C37 C38 118.5(8)
N1 C5 C4 103.4(7) C37 C38 Ru1 135.7(6)
C12 C11 N3 121.1(8) C42 C41 S1 117.8(7)
C12 C11 C16 121.7(8) C46 C41 S1 122.2(6)
C16 C11 N3 116.8(8) C46 C41 C42 120.0(7)
C11 C12 C13 118.4(9) C43 C42 C41 119.5(8)
C11 C12 C17 121.9(9) C42 C43 C44 122.1(8)
C13 C12 C17 119.7(9) C43 C44 C45 118.8(8)
C14 C13 C12 121.0(10) C43 C44 C47 124.2(8)
C13 C14 C18 119.5(11) C45 C44 C47 117.0(9)
C15 C14 C13 119.7(9) C46 C45 C44 117.8(8)
C15 C14 C18 120.8(11) C46 C45 C50 123.2(8)
C14 C15 C16 122.1(9) C50 C45 C44 119.0(8)
C11 C16 C19 122.9(8) C41 C46 C45 121.8(7)
C15 C16 C11 117.1(9) C48 C47 C44 121.0(9)
C15 C16 C19 120.0(9) C47 C48 C49 121.6(10)
C22 C21 N1 118.5(9) C50 C49 C48 120.0(10)
C26 C21 N1 119.1(8) C49 C50 C45 121.3(9)
S-66
Figure S28. Asymmetric fragment of compound 12h.
Table S21. Bond Lengths for 11h.
Ru1 Cl2 2.366(2) C22 C27 1.525(13)
Ru1 Cl1 2.334(2) C23 C24 1.380(14)
Ru1 S1 2.389(2) C24 C25 1.389(14)
Ru1 C2 2.063(9) C24 C28 1.534(13)
Ru1 C38 1.857(9) C25 C26 1.391(12)
S1 C31 1.761(9) C26 C29 1.537(13)
S1 C41 1.811(9) C31 C32 1.529(11)
N1 C2 1.346(10) C32 C33 1.426(12)
N1 C5 1.473(11) C32 C37 1.372(12)
N1 C21 1.428(10) C33 C34 1.400(12)
N3 C2 1.339(11) C34 C35 1.415(14)
N3 C4 1.492(10) C35 C36 1.355(13)
N3 C11 1.427(10) C36 C37 1.438(12)
C4 C5 1.509(12) C37 C38 1.500(13)
C11 C12 1.423(12) C41 C42 1.353(12)
C11 C16 1.406(12) C41 C46 1.419(13)
S-67
C12 C13 1.383(11) C42 C43 1.399(12)
C12 C17 1.501(12) C43 C44 1.383(13)
C13 C14 1.389(12) C43 C47 1.426(14)
C14 C15 1.400(12) C44 C45 1.417(13)
C14 C18 1.537(11) C44 C50 1.458(16)
C15 C16 1.383(12) C45 C46 1.329(13)
C16 C19 1.470(13) C47 C48 1.366(14)
C21 C22 1.404(12) C48 C49 1.431(16)
C21 C26 1.380(12) C49 C50 1.357(16)
C22 C23 1.403(12)
Table S22. Bond Angles for 11h.

Cl2 Ru1 S1 86.11(8) C26 C21 C22 121.9(8)
Cl1 Ru1 Cl2 162.54(8) C21 C22 C27 121.7(8)
Cl1 Ru1 S1 89.59(8) C23 C22 C21 118.4(8)
C2 Ru1 Cl2 92.3(3) C23 C22 C27 120.0(10)
C2 Ru1 Cl1 89.9(3) C24 C23 C22 120.2(9)
C2 Ru1 S1 173.0(3) C23 C24 C25 120.0(9)
C38 Ru1 Cl2 98.4(3) C23 C24 C28 119.5(10)
C38 Ru1 Cl1 98.3(3) C25 C24 C28 120.4(10)
C38 Ru1 S1 86.9(3) C24 C25 C26 121.2(9)
C38 Ru1 C2 100.0(4) C21 C26 C25 118.2(9)
C31 S1 Ru1 104.8(3) C21 C26 C29 120.3(9)
C31 S1 C41 100.6(5) C25 C26 C29 121.4(9)
C41 S1 Ru1 104.4(3) C32 C31 S1 110.1(7)
C2 N1 C5 113.5(7) C33 C32 C31 115.1(8)
C2 N1 C21 128.2(7) C37 C32 C31 125.1(8)
C21 N1 C5 118.4(6) C37 C32 C33 119.8(8)
C2 N3 C4 114.5(7) C34 C33 C32 120.7(9)
C2 N3 C11 127.0(7) C33 C34 C35 118.2(9)
S-68
C11 N3 C4 118.1(7) C36 C35 C34 121.5(9)
N1 C2 Ru1 131.4(7) C35 C36 C37 120.4(9)
N3 C2 Ru1 121.9(6) C32 C37 C36 119.4(8)
N3 C2 N1 106.7(7) C32 C37 C38 127.5(8)
N3 C4 C5 101.2(7) C36 C37 C38 113.1(8)
N1 C5 C4 103.9(7) C37 C38 Ru1 131.2(6)
C12 C11 N3 119.2(8) C42 C41 S1 123.7(8)
C16 C11 N3 119.8(8) C42 C41 C46 120.4(9)
C16 C11 C12 120.6(8) C46 C41 S1 115.4(8)
C11 C12 C17 123.5(8) C41 C42 C43 120.4(9)
C13 C12 C11 118.3(8) C42 C43 C47 119.9(9)
C13 C12 C17 117.8(8) C44 C43 C42 119.4(9)
C12 C13 C14 122.2(9) C44 C43 C47 120.7(9)
C13 C14 C15 118.3(7) C43 C44 C45 118.8(9)
C13 C14 C18 121.1(9) C43 C44 C50 120.2(11)
C15 C14 C18 120.6(8) C45 C44 C50 121.0(11)
C16 C15 C14 122.1(8) C46 C45 C44 121.6(9)
C11 C16 C19 121.2(8) C45 C46 C41 119.3(10)
C15 C16 C11 118.4(8) C48 C47 C43 118.9(10)
C15 C16 C19 120.2(9) C47 C48 C49 120.6(11)
C22 C21 N1 117.9(7) C50 C49 C48 121.9(11)
C26 C21 N1 120.1(8) C49 C50 C44 117.6(12)
S-69
Figure S29. Asymmetric fragment of compound 11h.
S-70
5. UV/Vis initiation kinetics
All catalyst solutions were prepared and handled without an inert atmosphere. Cuvettes were
tightly sealed and wrapped with additional parafilm to secure the cap. UV/Vis kinetics experiments
were performed on VARIAN CARY 50 spectrometer.
General procedure for UV/Vis initiation kinetics with ethyl vinyl ether (EVE).9
Scheme S10. Isomerization of complexes 11b,c,e, 11f−h in TCE-d2
A solution (1·10–4 M) of the appropriate catalyst 11f or 11h (0.01 mmol) in toluene (10.0 mL) was
prepared. Separately, a 3.0·10–2 M solution of EVE in toluene (10.0 mL) was prepared under
ambient atmosphere. The solution of the catalyst was placed in a cuvette (2 mL), then an aliquot
of the EVE solution (100 μL, 30 equiv) was added, and data collection was initialized. Spectra
were collected at regular intervals for at least three half-lives. The absorbance value at λmax was
plotted against time, and the data were fit to a first-order exponential decay function, from which
kinit was determined. The experiment was repeated in triplicate for each catalyst. The averaged
results are summarized in Table S23.
Figure S30. Representative data for an UV/Vis initiation kinetics experiment (catalyst 11h, trial
1). As the line number increases, the time from the start of the experiment increases.
S-71
0,55
0,5
0,45
0,4
Abs
0,35
0,3
0,25
0,2
0 0,5 1 1,5 2 2,5 3
Time, s ‧10^4
Figure S31. Representative plot of absorbance (λmax = 367 nm) versus time for an UV/Vis
initiation kinetics experiment (catalyst 11h, trial 1).
0
0 0,5 1 1,5 2 2,5 3 3,5
-0,1
-0,2
-0,3
Log (Abs)
-0,4
-0,5
-0,6
-0,7
-0,8
Time, s ‧10^4
Figure S32. Representative semi-log plot of absorbance (λmax = 367 nm) versus time for a UV/Vis
initiation kinetics experiment (catalyst 11h, trial 1).
Table S23. Summary of UV/Vis initiation kinetics data (kinit 10–4·s–1).
Catalyst λmax Trial 1 Trial 2 Trial 3 Average

11f 367 0.1250 0.1276 0.1233 0.1253
11h 360 0.1857 0.1890 0.1843 0.1633
S-72
6. References
(1) Polyanskii, K. B.; Alekseeva, K. A.; Raspertov, P. V.; Kumandin, P. A.; Nikitina, E. V.;
Gurbanov, A. V.; Zubkov, F. I. Hoveyda–Grubbs Catalysts with an N→Ru Coordinate Bond in a
Six-Membered Ring. Synthesis of Stable, Industrially Scalable, Highly Efficient Ruthenium
Metathesis Catalysts and 2-Vinylbenzylamine Ligands as Their Precursors. Beilstein J. Org.
Chem. 2019, 15, 769–779. https://doi.org/10.3762/bjoc.15.73
(2) Chang, A. B.; Lin, T.-P.; Thompson, N. B.; Luo, S.-X.; Liberman-Martin, A. L.; Chen, H.-Y.;
Lee, B.; Grubbs, R. H. Design, Synthesis, and Self-Assembly of Polymers with Tailored Graft
Distributions. J. Am. Chem. Soc. 2017, 139 (48), 17683–17693.
https://doi.org/10.1021/jacs.7b10525.
(3) SAINT-Plus (Version 7.68). Bruker AXS Inc., Madison, Wisconsin, USA (2007).
(4) Sheldrick G.M.: SADABS. Bruker AXS Inc., Madison, Wisconsin, USA (2008).
(5) Sheldrick G.M. A short history of SHELX. Acta Crystallogr. A, 2008, 64, 112–122.
https://doi.org/10.1107/S0108767307043930
(6) Sheldrick G.M. Crystal structure refinement with SHELXL. Acta Crystallogr. C, 2015, 71, 3–
8. https://doi.org/10.1107/S2053229614024218
(7) Dolomanov O. V. et al. OLEX2: A complete structure solution, refinement and analysis
program. J. Appl. Crystallogr. 2009, 42, 339–341. https://doi.org/10.1107/S0021889808042726
(8) Spek, A. L. PLATON SQUEEZE: a tool for the calculation of the disordered solvent
contribution to the calculated structure factors. Acta Cryst. 2015, C71, 9−18.
https://doi.org/10.1107/S2053229614024929
(9) Engle, K. M.; Lu, G.; Luo, S.-X.; Henling, L. M.; Takase, M. K.; Liu, P.; Houk, K. N.; Grubbs,
R. H. Origins of Initiation Rate Differences in Ruthenium Olefin Metathesis Catalysts Containing
Chelating Benzylidenes. J. Am. Chem. Soc. 2015, 137 (17), 5782–5792.
https://doi.org/10.1021/jacs.5b01144
S-73
7. Copies of NMR spectra of compounds 9, 11, 12
S-74
Formula C H S FW 206.3470
1H NMR spectrum of compound 9a
13 18
Acquisition Time (sec) 1.9818 Comment single_pulse Date

Date Stamp File Name Frequency (MHz) 600.17
Nucleus 1H Number of Transients 8 Origin ECA 600 Original Points Count 32768 Owner delta
Points Count 32768 Pulse Sequence single_pulse.ex2 Receiver Gain 30.00 Solvent CHLOROFORM-d
Spectrum Offset (Hz) 5391.4521 Sweep Width (Hz) 16534.39 Temperature (degree C) 22.500
3.76
0.89
0.88
0.90
7.21
7.20
2.46
2.47
2.44
1.56
1.38
1.35 1.36 1.37
5.67
5.70
5.35
5.33
5.33
7.21
5.67
5.69
1.54 1.55
7.50
1.58 1.57
7.51
7.10
7.08
7.11
7.13
7.23
7.19
7.23
0.00
0.94 1.02 0.99 1.00 2.01 1.99 2.04 2.03 3.05
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
Chemical Shift (ppm)
13 18

7.21
7.20
5.70
5.67
5.35
5.33
5.33
7.21
5.67
5.69
5.35
7.50
7.51
7.10
7.08
7.11
7.13
7.23
7.18 7.19
7.18 7.19
7.23
7.23
7.24
0.94 2.98 1.02 0.99 1.00
7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7 6.6 6.5 6.4 6.3 6.2 6.1 6.0 5.9 5.8 5.7 5.6 5.5 5.4 5.3
13 18

3.76
0.89
0.88
0.90
2.46
2.47
2.44
1.56
1.38
1.37
1.54 1.55
1.40
1.58 1.57
1.36
1.53
1.41
1.35
2.01 1.99 2.04 2.03 3.05
3.5 3.0 2.5 2.0 1.5 1.0

13C NMR spectrum of compound 9a
13 18
Acquisition Time (sec) 0.6921 Comment single pulse decoupled gated NOE Date
Date Stamp File Name
Frequency (MHz) 150.91 Nucleus 13C Number of Transients 725 Origin ECA 600
Original Points Count 32768 Owner delta Points Count 32768 Pulse Sequence single_pulse_dec
Receiver Gain 54.00 Solvent CHLOROFORM-d Spectrum Offset (Hz) 15091.3428
Sweep Width (Hz) 47348.49 Temperature (degree C) 23.300
22.14
13.80
127.72
126.23
116.07
31.62
134.28
34.07
135.54
130.15
76.95
77.38
137.01
77.16
192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0
13 18
127.72
126.23
127.51
116.07
134.28
135.54
130.15
137.01
138 137 136 135 134 133 132 131 130 129 128 127 126 125 124 123 122 121 120 119 118 117 116 115 114
13 18
22.14
13.80
31.62
31.65
34.07
34 33 32 31 30 29 28 27 26 25 24 23 22 21 20 19 18 17 16 15 14
1H NMR spectrum of compound 9b
Points Count 32768 Pulse Sequence single_pulse.ex2 Receiver Gain 30.00 Solvent CHLOROFORM-
d
0.96
0.97
3.74
2.34
2.36
7.21
5.35
5.33
5.70
5.67
5.33
7.50
7.22
7.52
1.78
0.00
7.24
7.11
7.08
7.10
1.80
1.77
7.13
7.20
1.76
1.81
1.54
4.65
1.82
1.75
1.03 0.95 1.03 1.00 2.07 1.98 0.95 6.06
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
d
7.21
5.35
5.33
5.70
5.70
5.35
5.67
5.33
5.67
7.50
7.22
7.52
7.24
7.11
7.08
7.10
7.13
7.20
7.20
7.24
1.03 2.98 0.95 1.03 1.00
7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7 6.6 6.5 6.4 6.3 6.2 6.1 6.0 5.9 5.8 5.7 5.6 5.5 5.4 5.3
d
0.96
0.97
3.74
2.34
2.36
1.78
1.80
1.77
1.76
1.81
1.54
1.82
1.75
2.07 1.98 0.95 6.06
3.5 3.0 2.5 2.0 1.5 1.0

13C NMR spectrum of compound 9b
22.15
34.59
41.13
28.51
127.50
126.21
116.06
134.32
127.72
130.18
137.05
77.15
77.36
76.94
208 200 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0
127.50
126.21
116.06
134.32
127.72
130.18
137.05
135.58
138 137 136 135 134 133 132 131 130 129 128 127 126 125 124 123 122 121 120 119 118 117 116
22.15
34.59
41.13
28.51
44 43 42 41 40 39 38 37 36 35 34 33 32 31 30 29 28 27 26 25 24 23 22 21 20
1H NMR spectrum of compound 9c
d
1.29
1.29
1.28
3.79
3.79
7.24
5.70
5.35
7.21
5.33 5.33
5.67
7.25
7.21
7.50
7.25
7.20
0.00
7.51
2.16
2.16
2.88
2.88
7.09
7.11
2.89
2.87
1.55
5.29
2.86
5.29
2.90
2.90
2.92
0.95 0.97 1.00 0.99 1.99 0.98 6.09
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
d
7.24
5.70
5.35
7.20 7.21
5.33
5.67
7.25
7.21
7.50
7.51
5.33
7.09
7.11
7.12
7.19 7.13
5.29
5.29
0.95 3.19 0.97 1.00 0.99
7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7 6.6 6.5 6.4 6.3 6.2 6.1 6.0 5.9 5.8 5.7 5.6 5.5 5.4 5.3
d
1.29
1.29
1.28
1.28
3.79
3.79
2.16
2.16
2.88
2.88
2.89
2.87
2.89
2.87
1.55
2.90
2.90
2.92
1.99 0.98 6.09
3.9 3.8 3.7 3.6 3.5 3.4 3.3 3.2 3.1 3.0 2.9 2.8 2.7 2.6 2.5 2.4 2.3 2.2 2.1 2.0 1.9 1.8 1.7 1.6 1.5 1.4 1.3 1.2
13C NMR spectrum of compound 9c
126.21
23.39
127.48
32.95
116.11
134.32
127.83
130.05
137.00
35.21
77.39
77.18
76.97
200 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0
126.21
127.48
116.11
134.32
127.83
130.05
137.00
135.55
138 137 136 135 134 133 132 131 130 129 128 127 126 125 124 123 122 121 120 119 118 117 116 115
23.39
32.95
35.21
77.39
77.18
76.97
75 70 65 60 55 50 45 40 35 30 25
1H NMR spectrum of compound 9d
d
1.40
3.80
1.39
5.28
7.21 7.21
5.69
5.36
5.72
5.72
5.69
7.28
7.20
7.50
7.49
7.11
7.09
7.14
7.30
0.01
0.90 0.95 1.00 1.00 2.06 11.08
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
d
7.21
7.28
7.29
7.20
7.50
7.49
7.22
7.11
7.09
7.21
7.14
7.12
7.30
7.50
7.29
7.25
7.19
7.23
7.19
0.90 3.16 7.23 0.95
7.55 7.50 7.45 7.40 7.35 7.30 7.25 7.20 7.15 7.10 7.05
d
3.80
5.28
5.69
5.36
5.72
5.34
5.72
5.36
5.34
1.00 1.00 2.06
5.7 5.6 5.5 5.4 5.3 5.2 5.1 5.0 4.9 4.8 4.7 4.6 4.5 4.4 4.3 4.2 4.1 4.0 3.9 3.8
13C NMR spectrum of compound 9d
13 18
Original Points Count 32768 Owner CKP Points Count 32768 Pulse Sequence single_pulse_dec
30.72
76.81
77.02
77.23
116.00
134.18
130.27
127.37
30.87
127.91
134.89
125.94
0.00
31.22
136.98
42.98
30.57
144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 -8
1H NMR spectrum of compound 9e
Formula C H OS FW 256.3626
16 16
Acquisition Time (sec) 1.9818 Comment single_pulse

Date
Frequency (MHz) 600.17 Nucleus 1H Number of Transients 8 Origin ECA 600
Original Points Count 32768 Owner CKP Points Count 32768 Pulse Sequence single_pulse.ex2
3.79
4.06
7.27
0.03
6.80
6.81
7.29
7.04
5.35
5.70
5.33
5.67
7.14
7.50
7.03
7.23
7.52
3.79
7.29
6.79
3.78
3.77
1.00 1.12 2.20 2.00 1.00 0.97 2.07 3.39
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 -0.5
16 16

Date
7.27
6.80
6.81
7.29
7.04
7.14
7.50
7.03
7.23
7.52
7.05
7.06
7.08
7.15
7.27
7.13
7.25
7.29
7.22
6.82
6.79
7.01
1.00 2.42 1.12 1.05 2.20 2.00
7.55 7.50 7.45 7.40 7.35 7.30 7.25 7.20 7.15 7.10 7.05 7.00 6.95 6.90 6.85 6.80 6.75 6.70 6.65 6.60 6.55
16 16

Date
3.79
4.06
5.35
5.70
5.33
5.67
3.79
3.78
3.77
1.00 0.97 2.07 3.39
5.9 5.8 5.7 5.6 5.5 5.4 5.3 5.2 5.1 5.0 4.9 4.8 4.7 4.6 4.5 4.4 4.3 4.2 4.1 4.0 3.9 3.8 3.7 3.6 3.5 3.4
13 NMR spectrum of compound 9e
16 16
130.25
114.40
127.54
116.09
77.04
77.25
76.83
125.97
134.08
38.99
134.71
127.58
55.29
58.09
136.92
159.34
133.96
0.00
125.72
160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0

13 NMR spectrum of compound 9e
16 16
130.25
114.40
127.54
116.09
125.97
134.08
134.71
127.58
128.13
134.40
136.92
129.16
115.97
133.96
125.72
140 138 136 134 132 130 128 126 124 122 120 118 116 114 112
1H NMR spectrum of compound 9f
d
4.15
7.16
7.31
7.25
7.32
5.70
5.67
5.32
5.32
5.34
5.67
7.16
7.32
7.49
7.15
7.51
7.06
0.00
7.07
7.04
1.52
0.95 1.90 0.98 1.00 1.00 2.00
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
d
7.16
7.31
7.25
7.31
7.32
7.31
7.22
7.24
7.27
7.16
7.32
7.19
7.20
7.24
7.49
7.15
7.51
7.06
7.07
7.23
7.04
7.09
7.17
7.32
7.20
7.24
7.22
7.17
7.19
7.26
7.18
7.30
0.95 1.90 5.95 0.98
7.50 7.45 7.40 7.35 7.30 7.25 7.20 7.15 7.10 7.05
d
4.15
5.70
5.67
5.32
5.32
5.34
5.67
5.34
5.70
1.00 1.00 2.00
5.7 5.6 5.5 5.4 5.3 5.2 5.1 5.0 4.9 4.8 4.7 4.6 4.5 4.4 4.3 4.2 4.1
13C NMR spectrum of compound 9f
128.98
127.90
130.21
116.53
126.21
37.10
134.13
76.95
77.37
77.16
136.56
130.31
137.24
200 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0
128.98
127.90
130.21
126.21
126.60
134.13
136.56
130.31
134.07
137.24
137.5 137.0 136.5 136.0 135.5 135.0 134.5 134.0 133.5 133.0 132.5 132.0 131.5 131.0 130.5 130.0 129.5 129.0 128.5 128.0 127.5 127.0 126.5 126.0
116.53
37.10
76.95
77.37
77.16
115 110 105 100 95 90 85 80 75 70 65 60 55 50 45 40 35

Formula C H NO S FW 271.3342
15 13 2

d
4.28
7.35
7.33
7.35
8.12
8.10 8.11
8.12
7.30
5.73
5.40
5.70
5.38
7.29
7.52
7.23
7.53
7.04
7.03
7.02
0.00
7.04
7.05
1.56
1.90 1.00 5.51 1.00 1.10 1.08 2.28
8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
15 13 2

d
7.35
7.33
7.35
8.12
8.10 8.11
7.33
8.12
7.30
7.29
7.52
7.23
7.31
7.53
7.24
7.28
7.04
7.03
7.02
7.04
7.05
7.02
7.06
7.06
7.22
7.25
1.90 1.00 5.51 1.00
8.15 8.10 8.05 8.00 7.95 7.90 7.85 7.80 7.75 7.70 7.65 7.60 7.55 7.50 7.45 7.40 7.35 7.30 7.25 7.20 7.15 7.10 7.05 7.00
15 13 2

d
19
4.28
5.73
5.40
5.70
5.38
1.10 1.08 2.28
5.8 5.7 5.6 5.5 5.4 5.3 5.2 5.1 5.0 4.9 4.8 4.7 4.6 4.5 4.4 4.3 4.2
13C NMR spectrum of compound 9e
15 13 2
130.06
117.27
126.77
123.97
128.42
126.50
35.07
76.82
77.03
133.61
77.24
131.90
137.42
147.41
145.33
0.00
200 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0
15 13 2
130.06
117.27
126.77
123.97
128.42
128.14
126.50
133.61
131.90
137.42
147.41
145.33
148 146 144 142 140 138 136 134 132 130 128 126 124 122 120 118 116
15 13 2
35.07
76.82
77.03
77.24
78 76 74 72 70 68 66 64 62 60 58 56 54 52 50 48 46 44 42 40 38 36 34
1H NMR spectrum of compound 9h
19 16
Acquisition Time (sec) 2.0972 Date Date Stamp

File Name Frequency (MHz) 700.17
Nucleus 1H Number of Transients 8 Origin Avance Original Points Count 32768
Owner nmr Points Count 65536 Pulse Sequence zg30 Receiver Gain 49.52
SW(cyclical) (Hz) 15625.00 Solvent CHLOROFORM-d Spectrum Offset (Hz) 6276.4883
4.19
0.00
7.50
7.51
7.25
7.49
7.36
7.05
5.69
5.32
5.30
5.67
7.74
7.10
7.09
7.76
7.84
7.22
7.85
8.41
8.40
7.37
7.04
7.54 7.53
0.94 0.96 0.96 2.85 1.00 0.99 2.01
8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
19 16

7.50
7.51
7.25
7.49
7.36
7.05
7.74
7.10
7.09
7.76
7.84
7.22
7.85
8.41
8.40
7.37
7.04
7.54 7.53
7.05
7.35
7.21
7.12
7.23
0.94 0.99 0.96 3.91 0.96 0.96 2.85
8.5 8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9
19 16

4.19
FZ9531_010001r
5.69
5.32
5.30
5.67
1.00 0.99 2.01
5.8 5.7 5.6 5.5 5.4 5.3 5.2 5.1 5.0 4.9 4.8 4.7 4.6 4.5 4.4 4.3 4.2 4.1 4.0 3.9
13C NMR spectrum of compound 9h
19 16

Nucleus 13C Number of Transients 400 Origin Avance Original Points Count 32768
Owner nmr Points Count 32768 Pulse Sequence zgpg30 Receiver Gain 101.00
76.83
77.01
77.19
116.32
37.32
126.19
127.83
126.46
126.02
127.69
125.18
125.54
130.27
127.75
129.66
137.13 134.00
133.90
1.03
0.00
136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0
13C NMR spectrum of compound 9h
19 16

Nucleus 13C Number of Transients 400 Origin Avance Original Points Count 32768
Owner nmr Points Count 32768 Pulse Sequence zgpg30 Receiver Gain 101.00
116.32
126.19
127.83
126.46
126.02
127.69
125.18
125.54
130.27
127.75
129.66
128.52
134.00
134.10
133.90
137.13
133.22
133.34
137 136 135 134 133 132 131 130 129 128 127 126 125 124 123 122 121 120 119 118 117 116 115
20
1.00 5674.65
19
18
17
16
15
14
1H
13
12
11
2307.58
2300.74
2299.27
10
2295.63
2288.88
2287.41
2285.10
9
2283.36
2277.51
2263.61
2261.81
8
2255.96
7.20 2254.64
2248.03
7.64 7 2157.75
2131.34
1.14 2124.53
2104.09
1966.99
6
1959.49
1609.72
NMR spectrum of compound 11a
3.06 1608.70
1607.71
5
1390.20
1.21 1375.98
1234.43
1227.32
4
6.44
1180.83
1166.52
758.22
749.12
3
734.45
23.19 721.60
686.46
665.81
2
13.45 581.44
573.49
559.80
17.70 555.78
1
388.97
379.45
371.44
1.48 368.32
360.88
353.55
349.29
ppm
2307.58
2300.74
2299.27
2295.63
8.0
2288.88
2287.41
2285.10
7.20 2283.36
2277.51
7.5
2263.61
2261.81
2255.96
2254.64
7.64 2248.03
2157.75
7.0
2131.34
2124.53
2104.09
1.14 1966.99
1959.49
6.5
6.0
1H
1609.72
5.5
3.06 1608.70
1607.71
5.0
1390.20
1.21 1375.98
4.5
1234.43
1227.32
6.44 1180.83
4.0
1166.52
3.5
3.0
758.22
749.12
23.19 734.45
2.5
721.60
686.46
665.81
581.44
2.0
573.49
13.45 559.80
555.78
388.97
379.45
1.5
371.44
368.32
360.88
17.70 353.55
349.29
1.0
345.93
225.46
218.37
211.53
0.5
1.48
28.75
ppm
350
314.20
300
250
13C
210.50
200
148.54
138.68
138.04
133.13
132.32
132.23
150
132.05
132.00
131.87
131.75
130.17
129.88
129.35
129.21
128.79
128.69
128.60
100
128.53
127.71
77.97
77.55
77.12
51.71
35.10
34.58
34.29
31.35
50
29.97
29.83
29.06
26.92
26.76
26.14
22.10
21.84
20.99
19.83
18.72
13.65
13.43
0 ppm
160
148.54
138.68
150
138.04
133.13
132.32
132.23
132.05
140
132.00
131.87
131.75
130.17
130
129.88
129.35
129.21
128.79
128.69
120
128.60
128.53
127.71
110
13C
100
90
77.97
80
77.55
77.12
70
60
51.71
50
35.10
34.58
40
34.29
31.35
29.97
29.83
29.06
30
26.92
26.76
26.14
22.10
20
21.84
20.99
19.83
18.72
13.65
10
13.43
0.86
ppm
350
314.18
300
250
200
132.31
150
132.00
131.87
129.35
129.20
128.78
128.68
128.59
128.52
100
DEPT-135 NMR spectrum of compound 11a
53.61
35.11
50
34.60
34.30
29.99
29.06
26.92
26.77
26.14
21.83
20.97
13.43
0 ppm
COSY NMR spectrum of compound 11a
ppm
0
10
12
14
16
18
20
20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
ppm
8
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm
NOESY NMR spectrum of compound 11a
ppm
10
12
14
16
18
20
20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
ppm
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm
HSQC NMR spectrum of compound 11a
ppm
50
100
150
200
250
300
21 20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
ppm
10
20
30
40
50
60
70
80
90
100
110
120
130
140
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm
HMBC NMR spectrum of compound 11a
ppm
50
100
150
200
250
300
20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
ppm
20
40
60
80
100
120
140
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm
20
1.00 5676.42
19
18
17
16
15
14
1H
13
12
11
2307.67
10
2300.59
2295.75
2288.73
2287.62
9
2284.98
2277.39
2260.88
2253.47
8
2246.14
6.59 2163.79
2156.37
7.53 7 2148.96
2120.36
1.14 2108.14
1962.46
1954.87
6
1608.85
1340.53
3.84 1326.66
1226.72
5
NMR spectrum of compound 11b
1202.17
1188.21
790.63
7.00 784.09
4
754.08
721.36
702.39
697.89
3
693.03
22.62 687.54
680.09
676.16
2
7.45 663.77
655.45
3.92 650.98
642.79
1
8.01 531.62
501.97
495.33
489.18
482.55
416.07
409.35
ppm
2307.67
2300.59
8.0
2295.75
2288.73
2287.62
6.59 2284.98
2277.39
7.5
2260.88
2253.47
2246.14
2163.79
7.53 2156.37
2148.96
7.0
2120.36
2108.14
1.14 1962.46
1954.87
6.5
6.0
5.5
1H
3.84 1608.85
5.0
1340.53
4.5
1326.66
7.00
1226.72
1202.17
4.0
1188.21
3.5 790.63
784.09
3.0
754.08
721.36
702.39
22.62 697.89
693.03
2.5
687.54
680.09
676.16
663.77
655.45
2.0
650.98
642.79
7.45 531.62
501.97
495.33
489.18
1.5
3.92 482.55
416.07
409.35
402.56
378.58
1.0
267.81
8.01 239.95
233.44
193.88
187.37
0.5
ppm
350
313.88
300
250
13C
210.36
200
148.77
138.68
150
132.18
132.00
131.87
129.35
129.15
128.68
128.53
100
54.49
54.13
53.77
53.40
50
53.04
39.48
35.43
26.33
26.15
21.83
21.38
21.01
0 ppm
160
148.77
150
138.68
140
132.18
132.00
131.87
129.35
130
129.15
128.68
128.53
120
110
13C
100
90
80
70
60
54.49
54.13
53.77
53.40
53.04
50
39.48
40
35.43
30
26.33
26.15
21.83
21.38
20
21.01
10 ppm
350
313.86
300
250
200
150
132.22
132.00
131.87
129.35
129.14
128.66
128.52
100
53.97
53.60
50
DEPT-135 NMR spectrum of compound 11b
39.49
35.45
26.34
21.83
21.38
20.99
0 ppm
COSY NMR spectrum of compound 11b
ppm
0
10
12
14
16
18
20
20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
ppm
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm
NOESY NMR spectrum of compound 11b
ppm
10
12
14
16
18
20
20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
NOESY NMR spectrum of compound 11b
ppm
8
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm
HSQC NMR spectrum of compound 11b
ppm
50
100
150
200
250
300
20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
ppm
20
30
40
50
60
70
80
90
100
110
120
130
140
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm
HMBC NMR spectrum of compound 11b
ppm
50
100
150
200
250
300
20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
ppm
20
30
40
50
60
70
80
90
100
110
120
130
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm
ppm
50
100
150
200
250
300
19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
ppm
20
40
60
80
100
120
140
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm
20
19
1.00 5672.46
18
17
16
15
14
13
1H
12
11
10
2236.81
2230.03
9
2229.46
2222.67
2186.96
2147.22
8
2131.34
2123.57
7.89 2120.24
2115.86
7
2111.83
1.05 2109.16
2080.05
1927.31
6
1919.84
1493.99
1482.16
1259.71
5
1.07
1251.03
1237.56
NMR spectrum of compound 11c
1226.12
4.16 1072.27
4
1060.30
1.11 977.40
1.07 970.71
963.96
3
957.20
950.54
19.53 840.39
800.30
2
757.71
733.10
3.43 695.73
666.38
1
635.35
3.02 370.09
363.49
144.09
137.22
ppm
8.5
8.0
2236.81
2230.03
2229.46
2222.67
7.5
2186.96
2147.22
7.89 2131.34
2123.57
2120.24
7.0
2115.86
2111.83
2109.16
2080.05
1.05 1927.31
6.5
1919.84
6.0
1H
5.5
1493.99
5.0
1.07 1482.16
4.5
1259.71
1251.03
4.16 1237.56
1226.12
4.0
1072.27
1.11 1060.30
3.5 977.40
970.71
1.07 963.96
957.20
950.54
3.0
840.39
800.30
757.71
2.5
19.53 733.10
695.73
666.38
635.35
2.0
1.5
3.43 370.09
363.49
1.0
3.02 144.09
137.22
0.5 ppm
315.39
300
250
211.46
13C
200
150.24
139.99
139.85
139.21
138.62
137.82
150
137.73
137.07
134.26
131.93
131.57
129.77
129.62
129.42
129.21
128.94
128.52
100
77.42
52.37
50.84
50
39.18
35.86
21.77
21.24
21.16
20.72
20.46
18.72
18.04
ppm
170
160
150.24
139.99
139.85
150
139.21
138.62
137.82
137.73
140
137.07
134.26
131.93
131.57
130
129.77
129.62
129.42
129.21
128.94
120
128.52
13C
110
100
90
80
77.42
70
60
52.37
50.84
50
40
39.18
35.86
30
21.77
21.24
21.16
20.72
20
20.46
18.72
18.04
10 ppm
315.36
300
250
200
150
131.92
129.77
129.62
129.42
129.19
128.92
128.52
100
52.38
50.85
50
DEPT-135 NMR spectrum of compound 11c
39.16
35.87
21.77
21.23
21.16
20.72
20.46
18.72
18.05
ppm
COSY NMR spectrum of compound 11c
ppm
10
12
14
16
18
20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 ppm
ppm
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm
NOESY NMR spectrum of compound 11c
ppm
10
12
14
16
18
20
20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 ppm
ppm
0
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm
HSQC NMR spectrum of compound 11c
ppm
50
100
150
200
250
300
20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
ppm
20
30
40
50
60
70
80
90
100
110
120
130
140
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm
HMBC NMR spectrum of compound 11c
ppm
50
100
150
200
250
300
19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
ppm
20
40
60
80
100
120
140
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm
20
1.00 5689.42
19
18
17
16
15
14
13
1H
12
11
10
9
2266.81
8
2259.64
2252.24
2150.51
8.43 7 2144.15
2137.64
2114.33
1964.00
1956.16
6
spectrum of compound 11d
2.52 1608.42
5
1239.98
4
5.29
851.58
3
782.44
773.53
18.86 758.52
749.12
2
724.67
9.91 317.12
1
299.87
ppm
8.5
8.0
2266.81
2259.64
7.5
2252.24
2150.51
2144.15
8.43 2137.64
2114.33
7.0
1964.00
1956.16
6.5
6.0
5.5
1H
1608.42
2.52
5.0
4.5
1239.98
4.0
5.29
3.5
3.0
851.58
782.44
773.53
18.86 758.52
2.5
749.12
724.67
2.0
1.5
9.91 317.12
299.87
1.0
0.5 ppm
315.75
300
250
211.98
13C
200
150.52
150
138.67
132.14
131.88
129.38
129.18
128.62
128.08
100
54.15
53.99
53.79
53.43
53.07
52.71
50
51.81
51.26
47.08
32.66
29.52
20.73
20.12
18.23
ppm
170
160
150.52
150
138.67
140
132.14
131.88
129.38
129.18
130
128.62
128.08
120
110
13C
100
90
80
70
54.15
60
53.99
53.79
53.43
53.07
52.71
50
51.81
51.26
47.08
40
32.66
29.52
30
20.73
20.12
20
18.23
10 ppm
DEPT-135 spectrum of compound 11d
315.74
131.88
129.38
129.17
128.62
128.08
32.66
29.52
20.73
300 250 200 150 100 50 ppm
COSY NMR spectrum of compound 11d
ppm
0
10
12
14
16
18
20
20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
COSY NMR spectrum of compound 11d
ppm
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
NOESY NMR spectrum of compound 11d
ppm
50
100
150
200
250
300
20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 ppm
NOESY NMR spectrum of compound 11d
ppm
20
30
40
50
60
70
80
90
100
110
120
130
140
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
HSQC NMR spectrum of compound 11d
ppm
50
100
150
200
250
300
20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 ppm
HSQC NMR spectrum of compound 11d
ppm
20
30
40
50
60
70
80
90
100
110
120
130
140
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
HMBC NMR spectrum of compound 11d
ppm
50
100
150
200
250
300
19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
HMBC NMR spectrum of compound 11d
ppm
20
40
60
80
100
120
140
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm
20
19
1.00 5663.72
18
17
16
15
14
1H
13
12
11
10
9
2243.14
2235.91
2228.58
2155.44
8
2148.12
1.28 2140.71
2108.08
8.66
7 2101.63
2089.47
3.19 2078.88
2070.45
1993.19
6
1.33
1984.70
1953.30
1945.62
1795.44
5
1.06 1477.54
NMR spectrum of compound 11e
1466.82
1230.17
5.25 1221.29
4
3.39 1215.32
1121.07
799.88
3
744.02
730.82
19.33 721.21
711.16
2
689.46
1.37 667.04
3.65 363.43
257.81
1
2.22 252.92
245.96
ppm
8.5
8.0
2243.14
2235.91
1.28 2228.58
7.5
2155.44
2148.12
2140.71
8.66 2108.08
2101.63
7.0
2089.47
2078.88
2070.45
3.19 1993.19
1984.70
6.5
1953.30
1945.62
1.33 1795.44
6.0
1H
5.5
1477.54
5.0
1.06
1466.82
4.5
5.25 1230.17
1221.29
1215.32
4.0
3.39 1121.07
3.5
3.0
799.88
744.02
19.33 730.82
2.5
721.21
711.16
689.46
667.04
2.0
1.37
1.5
3.65 363.43
257.81
1.0
2.22 252.92
245.96
0.5 ppm
315.07
300
250
209.73
13C
200
159.93
149.44
139.99
139.29
138.80
137.80
150
137.65
136.86
134.30
134.10
132.16
131.95
129.66
129.37
129.18
128.92
120.77
100
114.27
55.59
52.35
51.18
50
41.59
32.07
31.80
29.30
22.97
21.65
21.39
20.58
18.64
18.37
14.57
ppm
170
159.93
160
149.44
139.99
150
139.29
138.80
137.80
137.65
140
136.86
134.30
134.10
132.16
131.95
130
129.66
129.37
129.18
128.92
120
120.77
114.27
110
13C
100
90
80
70
60
55.59
52.35
51.18
50
41.59
40
32.07
31.80
30
29.30
22.97
21.65
21.39
20.58
20
18.64
18.37
14.57
10 ppm
315.05
312.02
300
256.06
250
200
185.59
174.34
150
134.81
134.09
132.16
129.65
129.37
129.17
128.92
114.27
100
74.44
74.26
74.04
73.98
73.67
73.61
55.59
52.35
DEPT-135 NMR spectrum of compound 11e
51.18
50
41.59
32.06
31.79
29.30
22.96
21.64
21.38
20.58
18.64
18.37
14.56
ppm
COSY NMR spectrum of compound 11e
ppm
10
12
14
16
18
20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 ppm
ppm
8
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
NOESY NMR spectrum of compound 11e
ppm
10
12
14
16
18
20
20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 ppm
ppm
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
HSQC NMR spectrum of compound 11e
ppm
50
100
150
200
250
300
20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
ppm
10
20
30
40
50
60
70
80
90
100
110
120
130
140
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
HMBC NMR spectrum of compound 11e
ppm
50
100
150
200
250
300
19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
ppm
20
40
60
80
100
120
140
160
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm
20
19
1.00 5652.82
0.14 5513.32
18
17
16
15
14
13
1H
12
11
10
2293.23
2285.34
2254.12
9
2246.86
2239.54
2191.85
2184.52
8
2177.29
2160.30
2150.37
15.59 7 2142.51
2134.97
2120.96
1.65 2114.05
2100.46
6
3.72 2092.72
1951.74
1943.97
1.40 1797.69
5
1561.10
1549.06
NMR spectrum of compound 11f
1238.43
1210.18
4
6.64 1198.03
857.08
827.49
811.13
3
753.30
722.71
22.43 710.59
690.24
2
670.91
642.40
619.05
5.10 540.05
1
527.90
475.65
372.58
362.95
258.62
252.20
245.24
ppm
8.5
2293.23
2285.34
8.0
2254.12
2246.86
2239.54
2191.85
7.5
2184.52
2177.29
15.59 2160.30
2150.37
2142.51
7.0
2134.97
2120.96
2114.05
2100.46
2092.72
6.5
1.65 1951.74
1943.97
3.72 1797.69
6.0
1H
5.5
1.40 1561.10
1549.06
5.0
4.5
1238.43
1210.18
1198.03
4.0
6.64
3.5
3.0
857.08
827.49
811.13
753.30
22.43 722.71
2.5
710.59
690.24
670.91
642.40
619.05
2.0
540.05
527.90
475.65
1.5
5.10 372.58
362.95
258.62
1.0
252.20
245.24
0.5 ppm
314.46
300
250
13C
209.64
200
149.61
145.91
139.84
139.42
138.85
138.16
137.78
150
136.83
136.06
134.24
133.28
133.02
132.25
131.52
131.38
131.24
130.71
129.65
100
129.19
128.88
52.34
51.19
50
40.04
34.25
22.63
21.63
21.38
20.62
20.40
19.43
18.72
18.30
14.50
ppm
170
160
149.61
145.91
139.84
139.42
150
138.85
138.16
137.78
136.83
136.06
140
134.24
133.28
133.02
132.25
130
131.52
131.38
131.24
130.71
120
129.65
129.19
128.88
13C
110
100
90
80
70
60
52.34
51.19
50
40.04
40
34.25
30
22.63
21.63
21.38
20.62
20.40
20
19.43
18.72
18.30
14.50
10 ppm
300
250
200
150
133.28
132.24
131.50
130.61
129.63
129.17
128.87
100
74.42
74.25
74.03
73.97
73.66
73.59
52.36
DEPT-135 NMR spectrum of compound 11f
51.19
50
40.04
21.64
21.37
20.64
18.72
18.30
ppm
COSY NMR spectrum of compound 11f
ppm
10
12
14
16
18
20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 ppm
ppm
8
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
NOESY NMR spectrum of compound 11f
ppm
10
12
14
16
18
20
20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 ppm
NOESY NMR spectrum of compound 11f
ppm
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
HSQC NMR spectrum of compound 11f
ppm
50
100
150
200
250
300
20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
ppm
20
30
40
50
60
70
80
90
100
110
120
130
140
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm
HMBC NMR spectrum of compound 11f
ppm
50
100
150
200
250
300
19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
ppm
20
40
60
80
100
120
140
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm
20
19
1.00 5619.48
0.04
18
17
16
15
14
13
12
1H
11
10
2388.94
9
2380.18
2262.53
2255.24
2247.85
8
2.45 2177.65
2171.20
2163.64
10.19 7 2156.04
2139.78
2130.98
1.18 2108.35
2080.65
6
1.29 2055.68
1950.36
1942.65
1.08 1794.09
5
1601.34
1590.12
1234.31
5.61 1214.09
4
1203.22
825.24
809.90
NMR spectrum of compound 11g
756.39
718.60
19.74 708.46
682.38
2
640.39
1.25 625.62
606.11
2.41 361.09
1
256.10
1.79 249.92
243.02
ppm
8.5
2.45 2388.94
8.0
2380.18
2262.53
2255.24
2247.85
2177.65
7.5
2171.20
2163.64
10.19 2156.04
2139.78
2130.98
7.0
2108.35
2080.65
2055.68
1950.36
1.18
6.5
1942.65
1.29 1794.09
6.0
5.5
1601.34
1.08 1590.12
1H
5.0
4.5
1234.31
5.61 1214.09
1203.22
4.0
3.5
3.0
825.24
809.90
756.39
19.74 718.60
2.5
708.46
682.38
640.39
625.62
606.11
2.0
1.25
1.5
2.41 361.09
1.0
256.10
249.92
1.79 243.02
0.5 ppm
313.18
300
250
208.33
200
13C
149.70
146.55
142.27
139.76
139.55
150
138.93
137.73
136.63
134.14
132.48
129.81
129.75
129.41
128.97
100 123.58
52.43
51.14
50
37.61
31.79
22.92
21.39
20.64
20.26
18.70
18.19
14.56
ppm
160
149.70
146.55
150
142.27
139.76
139.55
138.93
140
137.73
136.63
134.14
132.48
129.81
130
129.75
129.41
128.97
123.58
120
110
100
13C
90
80
70
60
52.43
51.14
50
40
37.61
31.79
30
22.92
21.39
20.64
20.26
20
18.70
18.19
14.56
10 ppm
313.16
300
250
200
146.55
135.41
134.35
150
132.47
131.95
131.22
130.72
129.80
129.40
128.96
126.73
124.17
123.57
100
77.64
74.44
74.24
73.95
73.59
52.42
51.15
50
37.61
31.78
29.40
22.91
21.38
DEPT-135 NMR spectrum of compound 11g
20.64
20.27
19.44
18.68
18.18
14.55
ppm
COSY NMR spectrum of compound 11g
ppm
10
12
14
16
18
20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 ppm
ppm
8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
NOESY NMR spectrum of compound 11g
ppm
10
12
14
16
18
20
20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 ppm
ppm
8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
HSQC NMR spectrum of compound 11g
ppm
50
100
150
200
250
300
20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
ppm
10
20
30
40
50
60
70
80
90
100
110
120
130
140
8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
HMBC NMR spectrum of compound 11g
ppm
50
100
150
200
250
300
19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
ppm
20
40
60
80
100
120
140
8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm
20
1.00 5704.24
19
18
17
16
15
14
13
2349.54
2348.40
2340.77
2337.44
1H
12
2334.56
2331.32
2328.38
2325.08
11
2321.66
2273.96
2265.29
2259.14
10
2255.60
2252.30
2249.44
2246.11
9
2244.22
2243.23
2236.66
2186.96
8
3.43 2173.84
4.47 2168.47
2165.65
8.24 2157.78
7
2150.28
1.05 2142.96
2128.76
2125.67
6
2123.87
2121.47
1.01 2117.03
2115.32
5
2103.04
2053.88
5.23 1979.03
1971.52
4
1608.67
NMR spectrum of compound 11h
1596.48
1304.06
1290.62
3
1278.31
18.96 1247.28
1246.50
1237.53
2
836.10
0.39 776.47
3.34 743.63
720.79
1
2.52
715.21
681.24
668.63
653.11
406.41
400.37
388.79
ppm
2337.44
2334.56
2331.32
2328.38
8.5
2325.08
2321.66
2273.96
2265.29
2259.14
8.0
2255.60
3.43 2252.30
2249.44
2246.11
4.47 2244.22
7.5
2243.23
2236.66
2186.96
2173.84
8.24 2168.47
7.0
2165.65
2157.78
2150.28
1.05 2142.96
2128.76
6.5
2125.67
2123.87
2121.47
2117.03
2115.32
6.0
2103.04
2053.88
1979.03
1971.52
5.5
1.01 1608.67
1H
1596.48
5.0
1304.06
4.5
1290.62
1278.31
5.23 1247.28
1246.50
1237.53
4.0
3.5
3.0
836.10
776.47
743.63
18.96 720.79
2.5
715.21
681.24
668.63
653.11
2.0
0.39
406.41
1.5
3.34 400.37
388.79
386.18
282.54
1.0
2.52 276.12
269.25
0.5 ppm
315.38
300
250
210.45
13C
200
149.97
139.41
138.80
137.90
136.95
134.10
133.16
132.79
132.31
150
131.52
130.57
129.66
129.56
129.32
128.88
128.80
128.27
127.97
127.71
127.24
100
126.67
126.43
125.96
125.42
77.69
77.47
77.26
76.84
52.31
51.19
50
39.16
31.79
22.88
21.28
20.58
20.31
18.66
18.40
14.45
ppm
170
160
149.97
139.41
138.80
137.90
136.95
150
134.10
133.16
132.79
132.31
140
131.52
130.57
129.66
129.56
130
129.32
128.88
128.80
128.27
127.97
120
127.71
127.24
126.67
126.43
110
125.96
13C
125.42
100
90
77.69
80
77.47
77.26
76.84
70
60
52.31
51.19
50
40
39.16
31.79
30
22.88
21.28
20.58
20.31
20
18.66
18.40
14.45
10 ppm
315.35
300
250
200
132.30
150
129.64
129.57
129.31
128.79
128.27
127.97
127.70
127.24
126.67
100
50 126.43
39.17
DEPT-135 NMR spectrum of compound 11h
31.79
22.87
21.28
14.44
ppm
COSY NMR spectrum of compound 11h
ppm
0
10
12
14
16
18
20
20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
ppm
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
NOESY NMR spectrum of compound 11h
ppm
10
12
14
16
18
20
20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 ppm
ppm
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
HSQC NMR spectrum of compound 11h
ppm
50
100
150
200
250
300
20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
ppm
10
20
30
40
50
60
70
80
90
100
110
120
130
140
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
HMBC NMR spectrum of compound 11h
ppm
50
100
150
200
250
300
19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
ppm
20
40
60
80
100
120
140
8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm
20
19
1.00 5468.34
18
17
16
15
14
13
1H
12
2260.34
2253.41
2246.02
2162.59
11
2157.45
2149.68
2141.79
2136.12
10
2130.20
2101.36
2093.62
1928.07
9
1920.53
1897.12
1608.10
1353.41
8
1341.46
1.28 1285.16
1273.66
5.51 7 1264.33
1253.52
1234.10
2.07 1230.59
1225.07
6
1221.35
1213.79
0.88 1209.34
1186.62
5
1182.12
1175.46
1171.23
6.95 1165.88
4
1162.40
1155.59
1145.06
1135.27
3
7.47 1124.23
1093.46
10.70 1081.46
949.85
2
945.62
934.30
8.98 931.81
924.73
1
4.46 920.02
873.62
839.46
718.03
706.63
692.49
647.77
ppm
8.5
8.0
2260.34
2253.41
1.28 2246.02
7.5
2162.59
2157.45
2149.68
5.51 2141.79
2136.12
7.0
2130.20
2101.36
2093.62
1928.07
6.5
2.07 1920.53
1897.12
1H
6.0
1608.10
1353.41
1341.46
1285.16
5.5
0.88 1273.66
1264.33
1253.52
1234.10
1230.59
5.0
1225.07
1221.35
1213.79
1209.34
4.5
1186.62
1182.12
1175.46
1171.23
6.95 1165.88
4.0
1162.40
1155.59
1145.06
1135.27
1124.23
3.5 1093.46
1081.46
949.85
945.62
934.30
3.0
7.47 931.81
924.73
920.02
873.62
839.46
2.5
718.03
10.70 706.63
692.49
647.77
507.43
2.0
500.14
495.63
488.19
482.70
8.98 445.03
1.5
430.18
423.39
418.26
411.51
404.73
1.0
4.46 397.52
390.35
382.88
307.03
300.01
292.78
285.42
277.32
0.5 ppm
300
293.14
250
13C
216.62
200
146.30
140.41
139.79
139.30
138.06
138.00
136.59
150
136.08
135.54
135.22
133.83
133.00
130.93
130.57
130.41
130.21
129.90
128.84
100
128.23
52.32
51.30
50
39.62
35.78
30.81
22.60
20.84
20.73
19.84
19.08
18.60
18.21
17.66
13.78
ppm
170
160
146.30
140.41
139.79
139.30
150
138.06
138.00
136.59
136.08
140
135.54
135.22
133.83
133.00
130
130.93
130.57
130.41
130.21
129.90
120
13C
128.84
128.23
110
100
90
80
70
60
52.32
51.30
50
NMR compound of compound 12a
39.62
40
35.78
30.81
30
22.60
20.84
20.73
19.84
20
19.08
18.60
18.21
17.66
13.78
10 ppm
300
293.09
250
200
150
130.94
130.56
130.20
129.87
128.85
128.23
100
52.30
51.30
50
39.63
35.79
DEPT-135 NMR spectrum of compound 12a
30.82
22.60
20.84
20.72
19.86
19.09
18.60
18.28
17.66
13.78
ppm
ppm
0
10
12
14
16
18
20
20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
ppm
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
ppm
10
12
14
16
18
20
20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 ppm
ppm
8
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm
ppm
50
100
150
200
250
300
19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
ppm
10
20
30
40
50
60
70
80
90
100
110
120
130
140
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
ppm
50
100
150
200
250
300
19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
ppm
10
20
30
40
50
60
70
80
90
100
110
120
130
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
ppm
50
100
150
200
250
300
19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
ppm
20
40
60
80
100
120
140
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm
20
19
1.00 5476.26
18
17
16
15
14
13
1H
12
2258.75
2251.43
2244.04
11
2162.65
2157.12
2149.26
2141.31
10
2136.03
2131.70
2123.90
2099.80
9
1927.25
1919.66
1898.53
1608.10
8
1363.07
1351.04
1.16 1294.73
5.70 7 1283.12
1273.75
1263.13
2.05 1236.39
1233.38
6
1227.44
1224.35
2.22 1216.31
1212.08
5
1189.09
1184.73
1178.10
5.76 1173.99
1168.32
1165.19
2.29 1160.54
1149.95
3
6.33 1140.10
1077.74
10.60 1065.64
992.20
2
986.56
6.11 978.18
972.51
877.73
1
6.68 862.66
1.20 843.52
720.94
705.34
698.67
689.43
571.30
564.87
ppm
8.5
8.0
2258.75
2251.43
1.16 2244.04
7.5
2162.65
2157.12
2149.26
5.70 2141.31
2136.03
7.0
2131.70
2123.90
2099.80
1927.25
6.5
2.05 1919.66
1898.53
6.0
1608.10
1363.07
1H
5.5
1351.04
2.22 1294.73
1283.12
1273.75
1263.13
5.0
1236.39
1233.38
1227.44
1224.35
1216.31
4.5
1212.08
1189.09
5.76 1184.73
1178.10
1173.99
4.0
1168.32
1165.19
1160.54
1149.95
1140.10
2.29 3.5 1077.74
1065.64
992.20
986.56
978.18
3.0
6.33 972.51
877.73
862.66
843.52
720.94
2.5
10.60 705.34
698.67
689.43
571.30
564.87
2.0
561.30
558.54
6.11 555.18
552.27
548.88
1.5
542.45
493.38
459.08
6.68 449.47
1.0
325.40
322.43
306.85
1.20 301.42
295.33
285.54
278.25
220.39
210.51
0.5 ppm
300
293.49
250
217.18
13C
200
146.25
139.58
139.33
138.10
138.02
136.49
150
136.17
135.52
134.13
133.13
130.97
130.48
130.34
130.28
129.95
129.86
128.81
100
128.22
54.15
52.71
52.34
51.36
50
42.78
39.34
26.25
22.42
20.82
20.71
19.95
19.12
18.77
17.75
ppm
170
160
146.25
139.58
139.33
150
138.10
138.02
136.49
136.17
140
135.52
134.13
133.13
130.97
130
130.48
130.34
130.28
129.95
129.86
120
128.81
128.22
110
13C
100
90
80
70
60
54.15
52.71
52.34
50
51.36
42.78
39.34
40
30
26.25
22.42
20.82
20.71
19.95
20
19.12
18.77
17.75
10 ppm
300
293.48
250
200
150
130.97
130.47
130.33
130.28
129.95
129.86
128.80
128.22
100
53.99
53.63
53.27
52.34
51.36
50
42.78
DEPT-135 NMR spectrum of compound 12b
39.34
26.25
22.41
20.81
20.70
19.95
19.12
18.76
18.37
17.76
ppm
ppm
0
10
12
14
16
18
20
20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
ppm
8
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
ppm
50
100
150
200
250
300
19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
ppm
20
30
40
50
60
70
80
90
100
110
120
130
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
ppm
50
100
150
200
250
300
19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
ppm
20
40
60
80
100
120
140
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm
20
19
1.00 5513.27
18
17
16
15
14
13
12
1H
11
2247.97
10
2240.65
2233.45
2163.49
2155.89
9
2148.69
2141.46
2133.98
2107.09
8
2095.21
2016.81
2009.22
9.77 7 1864.14
1608.25
1284.29
1.20 1270.63
1257.81
6
1206.58
1197.73
1.38 1182.54
1174.77
5
1166.58
1155.59
1030.98
1017.32
4
7.95 863.23
812.78
794.74
787.87
3
781.03
20.99 774.16
767.40
760.32
2
755.76
718.21
16.84 714.16
692.55
1
682.77
678.86
657.94
632.46
514.06
493.53
412.47
ppm
8.5
8.0
2247.97
2240.65
2233.45
7.5
2163.49
2155.89
9.77 2148.69
2141.46
2133.98
7.0
2107.09
2095.21
2016.81
2009.22
6.5
1.20 1864.14
6.0
5.5
1.38 1608.25
1H
5.0
1284.29
4.5
1270.63
1257.81
1206.58
1197.73
1182.54
4.0
7.95 1174.77
1166.58
1155.59
1030.98
1017.32
3.5 863.23
812.78
794.74
787.87
781.03
3.0
774.16
767.40
760.32
20.99 755.76
2.5
718.21
714.16
692.55
682.77
678.86
2.0
657.94
632.46
514.06
493.53
412.47
1.5
393.23
16.84 375.64
373.00
366.58
347.16
1.0
340.38
322.40
315.47
284.79
278.52
271.65
0.5 ppm
300
293.04
250
215.50
200
13C
145.26
139.68
139.19
138.13
136.95
135.76
150
135.24
134.89
133.76
131.85
130.53
130.17
129.78
129.48
129.40
128.79
128.56
100
128.21
52.12
51.54
39.72
50
34.52
31.56
29.66
22.55
20.81
20.62
20.02
19.28
18.90
18.01
13.84
ppm
170
160
145.26
139.68
139.19
150
138.13
136.95
135.76
135.24
140
134.89
133.76
131.85
130.53
130
130.17
129.78
129.48
129.40
128.79
120
128.56
128.21
110
13C
100
90
80
70
60
52.12
51.54
50
39.72
40
34.52
31.56
29.66
30
22.55
20.81
20.62
20.02
20
19.28
18.90
18.01
13.84
10 ppm
300
293.03
250
200
150
130.53
130.17
129.78
129.40
128.79
128.21
100
54.06
53.69
53.34
52.11
50
51.54
39.72
34.51
31.56
DEPT-135 NMR spectrum of compound 12c
22.54
20.81
20.03
19.29
18.87
18.01
ppm
ppm
0
10
12
14
16
18
20
20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
ppm
8
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
ppm
10
12
14
16
18
20
20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 ppm
ppm
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
ppm
50
100
150
200
250
300
19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
ppm
10
20
30
40
50
60
70
80
90
100
110
120
130
140
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
ppm
50
100
150
200
250
300
19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
ppm
20
40
60
80
100
120
140
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
20
19
1.00 5516.72
18
17
16
15
14
13
1H
12
2331.65
2322.80
2319.73
11
2273.42
2272.55
2265.98
2265.14
10
2258.54
2163.49
2155.95
2148.33
9
2142.00
2126.57
2115.80
2096.35
8
2046.71
3.88 2044.82
2037.82
8.50 7 1957.54
1949.94
1913.12
2.38 1798.20
1.13 1648.07
6
1635.80
1609.09
4.13 1608.16
1607.17
5
1271.83
1264.48
2.63 1260.10
1257.00
4
6.36 1244.34
1.35 1238.55
1236.03
1231.73
3
6.42 1226.69
1225.52
1166.70
1161.44
2
17.26 1154.33
1143.59
0.52 1137.61
1135.51
1
1058.11
1045.77
871.55
848.86
707.56
698.97
650.29
579.22
ppm
8.5
2331.65
2322.80
2319.73
8.0
2273.42
2272.55
3.88 2265.98
2265.14
2258.54
7.5
2163.49
2155.95
2148.33
8.50 2142.00
2126.57
7.0
2115.80
2096.35
2046.71
2044.82
2.38 2037.82
6.5
1957.54
1949.94
1913.12
1.13 1798.20
6.0
1648.07
1635.80
1H
5.5
4.13 1609.09
1608.16
1607.17
5.0
1271.83
1264.48
1260.10
1257.00
4.5
1244.34
2.63 1238.55
1236.03
1231.73
1226.69
4.0
1225.52
6.36 1166.70
1161.44
1154.33
1.35 1143.59
3.5 1137.61
1135.51
1058.11
1045.77
3.0
6.42 871.55
848.86
2.5
707.56
698.97
650.29
17.26
2.0
579.22
512.41
1.5
0.52 392.99
1.0
0.5 ppm
300
296.97
250
215.70
13C
200
160.68
146.18
139.24
138.22
136.12
136.03
135.84
150
134.93
133.72
133.08
130.60
130.24
130.14
129.95
129.79
129.57
128.10
100
122.22
114.14
55.35
54.15
53.79
53.43
53.07
50
52.71
52.29
51.20
46.48
20.80
20.74
19.78
19.10
18.23
17.85
ppm
170
160.68
160
146.18
139.24
150
138.22
136.12
136.03
135.84
140
134.93
133.72
133.08
130.60
130.24
130
130.14
129.95
129.79
129.57
120
128.10
122.22
114.14
13C
110
100
90
80
70
55.35
54.15
60 53.79
53.43
53.07
52.71
50
52.29
51.20
46.48
40
30
20.80
20.74
19.78
20
19.10
18.23
17.85
10 ppm
300
296.95
250
200
150
134.93
130.60
130.24
130.14
129.95
129.79
129.56
128.10
114.14
100
55.34
54.00
53.64
53.27
50
52.29
DEPT-135 NMR spectrum of compound 12e
51.20
46.47
20.80
19.79
19.10
18.24
17.86
ppm
ppm
0
10
12
14
16
18
20
20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
ppm
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm
ppm
50
100
150
200
250
300
19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
ppm
10
20
30
40
50
60
70
80
90
100
110
120
130
140
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 ppm
ppm
50
100
150
200
250
300
19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
ppm
20
30
40
50
60
70
80
90
100
110
120
130
140
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm
ppm
50
100
150
200
250
300
19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
ppm
20
40
60
80
100
120
140
160
8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm
20
19
1.00 5518.64
18
17
16
15
14
13
1H
12
2343.54
2335.91
2275.77
11
2268.29
2260.88
2236.00
2228.68
10
2221.23
2192.03
2184.20
9
2176.66
2167.69
2160.13
2152.62
8
2144.10
2132.90
10.62 2125.13
7 2120.93
1965.85
1958.23
2.09 1913.24
1773.86
6
1.01 1773.56
1658.76
6.74 1646.51
1608.88
5
1608.01
1272.88
1265.95
2.17 1261.06
4
1258.02
3.31 1245.42
1240.74
1237.71
3
6.04 1233.59
1228.52
1171.08
6.52 1168.71
2
1161.17
9.69 1154.00
1150.31
1079.66
1
1067.38
875.33
851.38
707.80
645.88
572.17
513.73
473.88
ppm
8.5
2343.54
2335.91
2275.77
2268.29
8.0
2260.88
2236.00
2228.68
2221.23
10.62
7.5
2192.03
2184.20
2176.66
2167.69
2160.13
7.0
2152.62
2144.10
2132.90
2125.13
2.09 2120.93
6.5
1965.85
1958.23
1913.24
1773.86
6.0
1.01 1773.56
1658.76
1646.51
1H
5.5
6.74 1608.88
1608.01
5.0
1272.88
1265.95
1261.06
1258.02
4.5
1245.42
1240.74
2.17 1237.71
1233.59
1228.52
4.0
1171.08
3.31 1168.71
1161.17
1154.00
3.5
1150.31
1079.66
1067.38
3.0
6.04 875.33
851.38
2.5
707.80
6.52
645.88
2.0
572.17
9.69 513.73
473.88
1.5
1.0
0.5 ppm
300
296.87
250
215.53
13C
200
146.16
139.35
138.24
136.11
135.93
135.81
150
133.75
133.45
133.14
131.36
130.62
130.25
129.97
129.61
129.14
128.66
100
128.18
54.12
52.68
52.27
50
51.22
46.15
20.82
19.78
19.10
18.17
17.84
ppm
170
160
146.16
139.35
150
138.24
136.11
135.93
135.81
140
133.75
133.45
133.14
131.36
130.62
130
130.25
129.97
129.61
129.14
120
128.66
128.18
13C
110
100
90
80
70
60
54.12
52.68
52.27
50
51.22
46.15
40
30
20.82
19.78
20
19.10
18.17
17.84
10 ppm
300
296.86
250
200
150
133.45
130.61
130.25
129.98
129.61
129.14
128.65
128.18
100
60.03
53.96
53.59
53.24
50
52.27
DEPT-135 NMR spectrum of compound 12f
51.22
46.14
20.82
19.77
19.10
18.17
17.84
ppm
ppm
0
10
12
14
16
18
20
20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
ppm
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm
ppm
50
100
150
200
250
300
20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
ppm
20
30
40
50
60
70
80
90
100
110
120
130
140
8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm
ppm
20
30
40
50
60
70
80
90
100
110
120
130
140
8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm
ppm
50
100
150
200
250
300
19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
ppm
20
40
60
80
100
120
140
8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm
20
19
1.00 5483.32
18
17
16
15
14
13
12
1H
11
2425.14
2416.26
2386.03
10
2377.15
2283.87
2277.18
2269.73
9
2174.86
2167.33
2159.77
2152.05
8
4.17
2143.86
1.22 2140.53
2129.75
4.15 7 1954.39
1946.88
1910.81
2.04 1782.86
1639.94
6
1.02 1627.91
1612.03
1.90 1609.39
1608.37
5
1607.32
1265.89
1254.15
1242.66
4
5.36 1238.01
1231.76
1225.37
1164.95
3
6.17 1157.42
1150.40
1137.79
14.33 1124.89
2
1112.76
874.40
843.82
0.79 708.37
1
694.62
636.07
582.85
508.39
493.29
276.15
ppm
8.5
2425.14
2416.26
4.17 2386.03
8.0
2377.15
2283.87
2277.18
1.22 2269.73
2174.86
7.5
2167.33
2159.77
4.15 2152.05
2143.86
7.0
2140.53
2129.75
1954.39
1946.88
6.5
2.04
1910.81
6.0
1.02 1782.86
1639.94
1627.91
5.5
1.90 1612.03
1609.39
1608.37
1H
1607.32
5.0
1265.89
4.5
1254.15
1242.66
1238.01
1231.76
1225.37
5.36
4.0
1164.95
1157.42
1150.40
1137.79
1124.89
3.5
3.0 1112.76
874.40
6.17 843.82
2.5
708.37
694.62
636.07
14.33
582.85
2.0
508.39
493.29
1.5
0.79
1.0
276.15
0.5 ppm
300
296.72
250
214.33
200
13C
147.87
145.91
139.79
139.44
138.58
138.41
138.18
150
135.91
135.60
134.47
133.47
133.14
131.11
130.53
130.38
130.06
129.75
129.68
100
128.60
123.25
54.24
52.80
52.35
50
51.40
45.73
20.79
20.72
19.75
19.12
18.17
17.83
ppm
170
160
147.87
145.91
139.79
139.44
150
138.58
138.41
138.18
135.91
140
135.60
134.47
133.47
133.14
131.11
130
130.53
130.38
130.06
129.75
120
129.68
128.60
123.25
110
13C
100
90
80
70
60
54.24
52.80
52.35
50
51.40
45.73
40
30
20.79
20.72
19.75
20
19.12
18.17
17.83
10 ppm
300
296.69
250
200
134.47
150
131.09
130.52
130.38
130.06
129.76
129.67
128.60
123.24
100
52.35
51.40
50
45.73
DEPT-135 NMR spectrum of compound 12g
20.72
19.76
19.12
18.17
17.82
ppm
ppm
0
10
12
14
16
18
20
20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
ppm
8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
ppm
10
12
14
16
18
20
20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 ppm
ppm
8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm
ppm
50
100
150
200
250
300
19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
ppm
10
20
30
40
50
60
70
80
90
100
110
120
130
140
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm
ppm
50
100
150
200
250
300
19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
ppm
20
40
60
80
100
120
140
8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
20
19
1.00 5529.93
18
17
16
15
14
13
12
2557.71
2383.30
2379.61
2374.15
11
2353.98
1H
2352.45
2345.16
2343.63
10
2340.95
2333.75
2291.40
9
2285.07
2281.23
1.02 2277.78
2271.44
8
2264.60
7.71 2172.13
2164.57
2157.03
4.42 7
2147.58
2138.28
2.06 2130.74
2093.83
6
1974.65
1967.02
3.23 1920.14
1673.37
5
1660.17
1608.34
1267.09
1263.10
4
5.45 1255.56
1251.21
1245.60
1240.14
3
6.21 1235.97
1161.98
1157.45
3.43
1152.98
2
1148.39
10.18 1143.77
1103.82
1091.48
1
882.83
855.46
711.88
569.89
522.50
479.79
ppm
9.0
2557.71
2383.30
2379.61
1.02 2374.15
8.5
2353.98
2352.45
2345.16
2343.63
2340.95
8.0
2333.75
7.71 2291.40
2285.07
2281.23
7.5
2277.78
2271.44
2264.60
4.42 2172.13
2164.57
7.0
2157.03
2147.58
2138.28
2130.74
2.06 2093.83
6.5
1974.65
1967.02
1920.14
6.0
1673.37
1660.17
5.5
3.23
1608.34
1H
5.0
1267.09
1263.10
1255.56
4.5
1251.21
1245.60
1240.14
1235.97
5.45
4.0
1161.98
1157.45
1152.98
1148.39
3.5 1143.77
1103.82
1091.48
882.83
3.0
6.21 855.46
2.5
3.43 711.88
2.0
569.89
10.18 522.50
479.79
1.5
1.0
ppm
297.11
300
250
215.51
200
146.23
139.52
13C
138.24
136.15
135.91
135.82
134.48
133.75
133.34
150
133.15
130.68
130.32
130.20
130.00
129.68
129.45
129.17
128.83
128.42
128.22
100
128.10
127.50
127.27
126.62
54.14
53.78
53.42
53.06
52.70
50
52.27
51.26
45.80
20.76
20.13
19.81
19.12
18.23
17.88
ppm
170
146.23
160
139.52
138.24
136.15
135.91
150
135.82
134.48
133.75
133.34
140
133.15
130.68
130.32
130.20
130.00
130
129.68
129.45
129.17
128.83
120
128.42
128.22
128.10
127.50
110
127.27
126.62
100
13C
90
80
70
54.14
60 53.78
53.42
53.06
52.70
50
52.27
51.26
45.80
40
30
20.76
20.13
19.81
20
19.12
18.23
17.88
10 ppm
297.10
300
250
200
134.48
130.67
130.32
130.20
150
130.00
129.82
129.68
129.45
129.17
128.83
128.21
128.10
127.50
127.27
126.62
100
52.27
51.26
50
45.81
20.74
20.13
19.82
19.11
DEPT-135 NMR spectrum of compound 12h
18.23
17.88
ppm
ppm
0
10
12
14
16
18
20
20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
ppm
9
8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm
ppm
10
12
14
16
18
20
20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 ppm
ppm
9
8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm
ppm
50
100
150
200
250
300
19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 ppm
ppm
20
30
40
50
60
70
80
90
100
110
120
130
140
8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm
ppm
50
100
150
200
250
300
19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
ppm
20
40
60
80
100
120
140
9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm

Om2c00556 Si 001

Uploaded by

Copyright:

Available Formats

Om2c00556 Si 001

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Om2c00556 Si 001

Uploaded by

Copyright:

Available Formats

Supporting Information

Properties and catalytic activity of Hoveyda-Grubbs-type

2.1 Ligand synthesis

Scheme S1. Synthesis of 2-vinylbenzylchloride 8

N,N-Вimethyl-2-vinylbenzylamine 7 was prepared according to a previously reported

Scheme S2. Synthesis of benzylidene ligands 9

2-Vinylbenzyl butyl sulfide (9a)

2.2 Synthesis of trans-complexes 11

Scheme S3. Synthesis of trans-complexes 11a−h

2.3 Synthesis of cis-complexes 12

Scheme S4. Synthesis of cis-complexes 12a−c, 12e−h

Figure S1. 11a (left) and 12a (right) complexes.

2.4 Activity of 11 in RCM reactions

Scheme S5. RCM reactions of 15, 17, 19 promoted by 11 complexes in CHCl3

11a (R1 = nBu)

11e, r.t, (R1 = 4-MeOC6H4)

11e, D, (R1 = 4-MeOC6H4)

60 11e (R1 = 4-MeOC6H4)

2.6 Activity of 12 in RCM reactions with N,N-diallyltosylamide

12c (R1 = iPr)

60 12e (R1 = 4-MeOC6H4)

2.7 Activity of 12 in RCM reactions under photochemical activation

12e (R1 = 4-MeOC6H4)

60 12f (R1 = Ph)

2.8 Polymerization of norborn-5-ene-2,3-dicarboxylic acid dibutyl ester (NBBA)

Scheme S8. ROMP polymerization of NBBA2 promoted by 11d−h catalysts.

11d (R1 = tBu)

3.1 Isomerization of 11 in TCE-d2 and CDCl3

Scheme S9. Isomerization of complexes 11b,c,e, 11f−h in TCE-d2

60 11b→12b at 70 ℃ (R1= iBu)

Figure S9. NMR kinetics of isomerisation of complexes 11b,c,e, 11f−h in TCE-d2.

4.2. Tables and Figures

Table S3. Bond Lengths for 12a.

Table S4. Bond Angles for 12a.

C14 C13 C12 122.6(3) C42 C41 S1 111.3(2)

C13 C14 C18 120.8(3) C43 C42 C41 114.5(3)

C15 C14 C13 118.3(3) C42 C43 C44 116.0(3)

C15 C14 C18 120.9(3)

Atom Atom Length/Å Atom Atom Length/Å

Ru1 Cl1 2.4066(18) Ru2 C2A 2.018(7)

Ru1 Cl2 2.4066(18) Ru2 C38A 1.832(7)

Ru1 S1 2.3293(18) S1A C37A 1.822(7)

Ru1 C2 2.023(6) S1A C41A 1.828(8)

N3 C2 1.353(8) C4A C5A 1.532(10)

N3 C4 1.477(9) C11A C12A 1.377(9)

N3 C11 1.415(9) C11A C16A 1.411(10)

C4 C5 1.548(10) C12A C13A 1.398(10)

C11 C16 1.391(10) C13A C14A 1.399(10)

C12 C13 1.399(11) C14A C15A 1.386(10)

C12 C17 1.476(11) C14A C18A 1.530(10)

C13 C14 1.387(12) C15A C16A 1.371(10)

C14 C15 1.403(11) C16A C19A 1.499(10)

C14 C18 1.495(11) C21A C22A 1.389(10)

C15 C16 1.389(10) C21A C26A 1.418(10)

C16 C19 1.511(10) C22A C23A 1.393(10)

C21 C22 1.403(10) C22A C27A 1.506(10)

C21 C26 1.415(10) C23A C24A 1.370(11)

C22 C23 1.368(10) C24A C25A 1.382(12)

C22 C27 1.512(10) C24A C28A 1.522(11)