Iridium N-heterocyclic carbene complexes as efficient catalysts for magnetization

transfer from parahydrogen: A route to substrate sensitization in NMR and MRI

Michael
b
J. Cowleya, Ralph W.
c
Adamsa, Martin C. dR. Cocketta, Simon
d
B. Duckett,a* Garya G. R.
Green , Joost A. B. Lohman , Rainer Kerssebaum , David Kilgour and Ryan E. Mewis
a
Department of Chemistry, University of York, Heslington, York, YO10 5DD, UK
b
York Neuroimaging Centre, The Biocentre, York Science Park, Heslington, York, YO10 5DG, UK
c
Bruker UK, Limited, Banner Lane, Coventry, CV4 9GH,UK
d
Bruker BioSpin GmbH, Silberstreifen 4, 76287 Rheinstetten, Germany
RECEIVED DATE (automatically inserted by publisher); E-mail: [email protected]

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 Supplementary information

1. General Considerations ........................................................................................ 3s

2. Synthetic procedures ............................................................................................ 3s
3. Sample Preparation .............................................................................................. 4s
4. Sample Polarization ............................................................................................. 4s
5. Evaluation of catalyst loading.............................................................................. 5s
6. Effect of para-H2 pressure ................................................................................... 5s
7. Kinetics of H2 and Py Exchange in [4a]Cl........................................................... 5s
8. Calculation of enhancement factors..................................................................... 6s
9. Field dependent polarisation studies.................................................................... 9s
10. X-Ray Structure of 4a[PF6]............................................................................ 10s
11. DFT Calculations ........................................................................................... 29s
12. Cartesian Coordinates, total electronic energies + zero point energies, enthalpies
and free energies ........................................................................................................ 30s

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1. General Considerations

All experimental procedures were performed under an atmosphere of either dinitrogen or

argon, using standard Schlenk line techniques or an MBraun Unilab glovebox, unless
otherwise stated. General solvents for synthetic chemistry were dried using an Innovative
Technology anhydrous solvent engineering system or were distilled from an appropriate
drying agent under N2 as necessary. Deuterated solvents (d4-methanol, d6-acetone,
CDCl3) were obtained from Sigma-Aldrich and used as supplied.

NMR measurements were made on a Bruker Avance III series 400 MHz NMR
spectrometer (1H at 400.13 MHz, 31P at 161 MHz, 15N at 40 MHz) or a Bruker Avance II
series 700 MHz (1H at 700.13 MHz, 31P at 282 MHz, 15N at 70 MHz). NMR samples
were made up in Young’s tap equipped 5 mm NMR tubes.

2. Synthetic procedures

[IrCl(cod)(IMes)], 2, and 3,4,5-trideuteriopyridine were prepared according to published

literature methods. 1,2

3. Sample Preparation

Samples for the substrate polarisation tests were typically prepared as follows:

The substrate to be polarised (0.062 mmol) was dissolved in d4-methanol (400 µl). To
this solution was added 0.0031 mmol of catalyst (for example, with [IrCl(cod)(IMes)],
200 µL of a 10mg/mL solution was added). The resulting solutions were then taken up
by syringe and transferred into a Young’s tap NMR tube. The sample was then degassed
on a high-vacuum line via three ‘cool’-pump-thaw cycles (the sample was cooled to –78
۫°C rather than frozen in liquid N2 to avoid cracking of the NMR tube upon thawing).
Parahydrogen, at a pressure of 3.0 atmospheres was then admitted to the NMR tube.

4. Sample Polarization

A sample was prepared as described above. The sample was shaken (to replenish the
parahydrogen level in solution) for approximately 5 seconds and rapidly (within 5
seconds) inserted into the NMR spectrometer, after which NMR spectra were
immediately acquired. After several shakes, the parahydrogen is usually depleted,
resulting in lower signal enhancement. Replenishing the parahydrogen in the NMR tube
at this stage restores the original degree of enhancement.

1
Vazquez-Serrano, L. D.; Owens, B. T.; Buriak, J. M. Inorg. Chim. Acta 2006, 359, 2786.
2
Pavlik, J. W.; Laohhasurayotin, S. J. Heterocycl. Chem. 2007, 44, 1485.

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5. Evaluation of catalyst loading

The effect of catalyst loading on the degree of enhancement observed for pyridine
was investigated. A range of samples were prepared, each comprising of 600 µL of a
methanol solution of the catalyst and pyridine, with catalyst and substrate
concentrations as detailed below in
Table s1. Each sample was then degassed before 3 atmosphere of parahydrogen was
admitted. The initial reaction with H2 was monitored by 1H NMR spectroscopy until
complete consumption of the iridium starting material [IrCl(cod)(IMes)] had occurred. At
this point the sample is activated. The sample was then degassed and 3 atm. of fresh
parahydrogen admitted. The sample was then shaken at earth’s magnetic field for 10
seconds before being rapidly inserted into the spectrometer where a single scan 1H NMR
spectrum was acquired. After complete relaxation of the polarisation a second NMR
spectrum was obtained with the same acquisition parameters in order to measure the
signal due to thermal polarisation. The enhancements were then calculated as described in
section six of this document.

For each sample, three polarisation/measurement steps were completed and the
calculated enhancements from each step averaged to give the values presented below
in
Table s1.

Catalyst [IrCl(cod)(Imes)
Sample loading [Py] / mM ] / mM sub:cat ratio
1 0.1% 103.45 0.10 1000
2 0.5% 103.45 0.52 200
3 1.0% 103.45 1.03 100
4 1.5% 103.45 1.55 67
5 2.0% 103.45 2.07 50
6 2.5% 103.45 2.59 40
7 5.0% 103.45 5.17 20
8 10.0% 103.45 10.34 10

Table s1: Catalyst and substrate concentration for studies on the effect of substrate :
catalyst ratio on the degree of enhancement observed for pyridine. The total volume of
all samples was always 600 µL. Table s2 contains the matching signal enhancements.

1 1 1
mol % ortho H meta H para H
cat resonance resonance resonance
0.10 -8 4 -7
0.50 -19 10 -15
1.00 -41 20 -32
1.50 -58 29 -47

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 2.00 -59 35 -48
2.50 -138 101 -121
5.00 -235 191 -195
10.00 -367 327 -357

Table s2: Effect of the catalyst loading (precatalyst used was [IrCl(cod)(IMes)]) on the
pyridine 1H enhancements for the indicated sites when the reaction occurs in the earth’s
magnetic field.

6. Effect of para-H2 pressure

The effect of the parahydrogen pressure on the degree of enhancement observed for the
two meta protons of pyridine was then investigated. A sample was prepared containing
600 µL of a d4-methanol solution which was 103.45 mM in pyridine and 5.17 mM in
[IrCl(cod)(IMes)]. This sample was then polarised for a series of reactions at a range of
pressures of parahydrogen and the degree of enhancement observed at each pressure was
quantified. These data are summarised in Figure s1

Enhancement of Meta Resonance of Pyridine

300.00

250.00
enhancement factor

200.00

150.00

100.00

50.00

0.00
1 1.5 2 2.5 3
pressure of p-H2 / atm

Figure s1. Effect of parahydrogen pressure on the level of signal enchantment.

7. Kinetics of H2 and pyridine exchange in [4a]Cl

The activation parameters for H2 and pyridine exchange in [4a]Cl are presented below in
Table s3. The rate data used in obtaining these values for these processes at a range of

5S
temperatures are presented in Tables s4 and s5. Eying plots are shown in Figure s2 and
Figure s3 The activation parameters use twice the rate constants for of forward reaction
in order to take into account reversibility at the transition state.3

Pyridine exchange Hydrogen exchange

∆H‡ 93 ± 3 kJ mol-1 79 ± 1 kJ mol-1

∆S‡ 97 ± 9 J K-1 mol-1 41 ± 3 J K-1 mol-1

Table s3: Pyridine and H2 exchange activation parameters for [4a]Cl

rate
constant
-1
T /s
268 K 0.11
275 K 0.32
280 K 0.78
285 K 1.19
290 K 2.73
295 K 5.93
300 K 11.79

Table s4: Pyridine dissociation rates for [4a]Cl

0
3.3000E- 3.3500E- 3.4000E- 3.4500E- 3.5000E- 3.5500E- 3.6000E- 3.6500E- 3.7000E- 3.7500E- 3.8000E-
03 03 03 03 03 03 03 03 03 03 03
-1

-2

-3
ln 2k/T

-4

-5

-6

-7
1/T

Figure s2: Eyring plot for pyridine dissociation in [4a]Cl

3
M. L. H. Green, L. L. Wong and A. Sella, Organometallics, 1992, 11, 2660

6S
 Observed
-1
T rate / s
300 8.89
295 4.89
290 2.73
280 0.84
275 0.44
270 0.23

Table s5: observed H2 dissociation rates for [4a]Cl

0
3.3333E-03 3.3898E-03 3.4483E-03 3.5088E-03 3.5714E-03 3.6364E-03 3.7037E-03
-1

-2

-3
ln k/T

-4

-5

-6

-7

-8
1/T

Figure s3: Eyring plot for H2 dissociation in [4a]Cl

8. Calculation of enhancement factors

1
H Enhancement Factors:

For calculation of the enhancement of 1H NMR signals the following formula was used:

E = enhancement
Spol = signal of polarized sample

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Sunpol = signal of unpolarized (reference) sample

Experimentally, the reference spectra were acquired with the same sample that was used
for the hyperpolarised measurement after it had fully relaxed (typically 5-10 minutes at
high magnetic field). Reference and polarized spectra were collected using identical
acquisition parameters, particularly the receiver gain. The raw integrals of the relevant
resonances in the polarized and unpolarized spectra were used to determine the
enhancement level.

9. Field dependent polarisation transfer studies

In order to complete these studies a flow system was designed to enable a solution
containing the catalyst [IrCl(cod)(IMes)] and the nitrogen heterocycle pyridine to be
polarised using parahydrogen within a reaction chamber outside the main NMR magnet.
This solution was then transferred into the Bruker Avance III series 400 MHz
spectrometer for interrogation in a NMR flow probe. Once interrogated, the solution
could be returned to a polarising chamber and this process repeated as required. A coil
surrounded the reaction chamber such that a magnetic field could be generated in the z
direction. This coil was designed to produce static DC fields in the range of -150 to 150
G.

The reaction chamber contained a solution comprising [IrCl(cod)(IMes)] (10 mg), the
nitrogen heterocycle (0.31 mmol), and 3 mL d4-methanol. Parahydrogen, prepared by
cooling hydrogen gas over charcoal in a copper block at 30 K, was then bubbled through
the solution at a pressure of 2 bar for ten seconds before this flow was stopped. The
solution was then allowed to settle for one second before transferring into the TXO flow
probe head (flow cell volume 200 µl) that was located within the NMR system. Once the
solution had transferred into the NMR flow probe head it was allowed to settle for 1 s
before a single scan 1H NMR spectrum was collected. In order to probe the signal
intensity variation with the magnetic field experienced by the sample during the reaction,
a series of 1H NMR spectra were collected, in steps of 5 G. Five NMR spectra were
collected at each point to ensure reproducibility. The solution was allowed to equilibrate
for five minutes to ensure that the polarisation level had decayed to its thermal
equilibrium value between each run.

The following figures highlight the effect of the magnetic field on the polarisation
transfer from parahydrogen. This clearly results in a substantial variation in the degree of
signal enhancement when compared with the same NMR spectrum collected under
normal, thermal, conditions. The resonances shown in Figures s4 - s6 were recorded in
the same experiment (i.e. the data for the different resonances are extracted from a single
1
H trace at each magnetic field).

8S
Figure s4: Intensity of the ortho pyridine resonance, of over the polarization transfer
field range of 0 to +150 G. Spectra were recorded in steps of 5 G.

Figure s5: Intensity of the para pyridine resonance, of over the polarization transfer field
range of 0 to +150 G. Spectra were recorded in steps of 5 G.

9S
Figure s6: Intensity of the meta pyridine resonance, of over the polarization transfer field
range of 0 to +150 G. Spectra were recorded in steps of 5 G.

10. X-Ray Structure of 4a[PF6]

Crystals of 4a[PF6] were grown by preparing a saturated solution of

[Ir(cod)(MeCN)(IMes)]PF6 in methanol (0.6 mL). Pyridine (3 µL) was then added to this
solution, which was subsequently degassed and placed under 3 atm. of H2. Crystals
formed on standing at room temperature for several days.

X-ray data were obtained for a crystal of 4a[PF6] at 110 K using a Bruker Smart Apex
diffractometer with Mo Kα radiation (ν = 0.71073 Å) in conjunction with a SMART
CCD camera. Diffractometer control, data collection and initial unit cell determination
was performed using “SMART” (v5.625 Bruker-AXS). Frame integration and unit-cell
refinement software was carried out with the “SAINT+” (v6.22, Bruker AXS) package.
Absorption corrections were applied by SADABS (v2.03, Sheldrick). The structure was
solved via a Patterson map using ShelXS (Sheldrick, 1997) and refined using ShelXL
(Sheldrick, 1997).

10S
Figure s7: ORTEP plot of the cation of 4a[PF6].MeOH in the solid state. Ellipsoids are
set at 50 % probability; hydrogen atoms and solvent molecules are omitted for clarity.
Selected bond lengths (Å) and angles (°): C1–Ir1 1.989(3), Ir1–N1 2.220(3), Ir1–N2
2.192(3), Ir1–N3 2.129(3), C1–Ir1–N3 173.55(12), C1–Ir1–N2 93.89(12), C1–Ir1–N1
102.17(12), N3–Ir1–N1 83.10(11), N2–Ir1–N1 96.80(11).

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Table s6. Crystal data and structure refinement for 4a[PF6].
Identification code sbd0901
Empirical formula C37 H45 F6 Ir N5 O P
Formula weight 912.95
Temperature 110(2) K
Wavelength 0.71073 Å
Crystal system Orthorhombic
Space group Pbca
Unit cell dimensions a = 14.6676(8) Å α= 90°.
b = 18.9334(11) Å β= 90°.
c = 27.3174(16) Å γ = 90°.
Volume 7586.2(8) Å 3
Z 8
Density (calculated) 1.599 Mg/m3
Absorption coefficient 3.628 mm-1
F(000) 3648
Crystal size 0.26 x 0.21 x 0.10 mm3
Theta range for data collection 1.49 to 28.32°.
Index ranges -19<=h<=19, -25<=k<=25, -36<=l<=36
Reflections collected 75388
Independent reflections 9444 [R(int) = 0.0410]
Completeness to theta = 28.32° 99.9 %
Absorption correction Semi-empirical from equivalents
Max. and min. transmission 0.696 and 0.480
Refinement method Full-matrix least-squares on F2
Data / restraints / parameters 9444 / 0 / 476
Goodness-of-fit on F2 1.031
Final R indices [I>2sigma(I)] R1 = 0.0310, wR2 = 0.0736
R indices (all data) R1 = 0.0447, wR2 = 0.0815
Largest diff. peak and hole 2.058 and -0.877 e.Å-3

12S
Table s7. Atomic coordinates ( x 104) and equivalent isotropic displacement
parameters (Å2x 103) for 4a[PF6]. U(eq) is defined as one third of the trace of the
orthogonalized Uij tensor.
____________________________________________________________________
x y z U(eq)
_____________________________________________________________________
C(1) 6572(2) 2585(2) 3717(1) 22(1)
C(2) 5142(3) 2912(2) 3468(2) 31(1)
C(3) 5479(3) 3451(2) 3727(2) 32(1)
C(4) 6899(2) 3697(2) 4184(1) 24(1)
C(5) 7456(2) 4200(2) 3956(1) 25(1)
C(6) 7973(2) 4639(2) 4265(2) 29(1)
C(7) 7934(3) 4581(2) 4771(2) 31(1)
C(8) 7355(3) 4083(2) 4981(2) 32(1)
C(9) 6823(2) 3633(2) 4690(1) 28(1)
C(10) 7471(3) 4288(2) 3413(1) 30(1)
C(11) 8512(3) 5063(2) 5088(2) 42(1)
C(12) 6174(3) 3115(2) 4919(2) 37(1)
C(13) 5640(2) 1715(2) 3230(1) 24(1)
C(14) 5377(2) 1143(2) 3520(1) 24(1)
C(15) 5242(2) 497(2) 3290(1) 28(1)
C(16) 5346(2) 415(2) 2786(1) 31(1)
C(17) 5552(2) 1007(2) 2511(1) 30(1)
C(18) 5684(2) 1668(2) 2721(1) 28(1)
C(19) 5212(3) 1224(2) 4060(1) 30(1)
C(20) 5186(3) -293(2) 2543(2) 42(1)
C(21) 5795(3) 2314(2) 2403(2) 37(1)
C(22) 9265(3) 3126(2) 3593(1) 28(1)
C(23) 10049(3) 3509(2) 3680(2) 34(1)
C(24) 10313(3) 3638(2) 4156(2) 36(1)
C(25) 9770(3) 3381(2) 4525(2) 34(1)
C(26) 8994(3) 3000(2) 4413(1) 28(1)
C(27) 8075(3) 1149(2) 2924(2) 33(1)
C(28) 8171(3) 955(3) 2442(2) 44(1)
C(29) 8165(3) 1464(3) 2084(2) 46(1)

13S
C(30) 8058(3) 2158(3) 2223(2) 39(1)
C(31) 7955(2) 2318(2) 2716(1) 28(1)
C(32) 8692(3) 847(2) 4371(2) 31(1)
C(33) 9368(3) 360(2) 4484(2) 37(1)
C(34) 10195(3) 392(2) 4242(2) 35(1)
C(35) 10327(3) 918(2) 3900(1) 33(1)
C(36) 9612(3) 1375(2) 3799(1) 29(1)
Ir(1) 7693(1) 2023(1) 3846(1) 19(1)
N(1) 8736(2) 2860(2) 3950(1) 23(1)
N(2) 7964(2) 1830(2) 3068(1) 24(1)
N(3) 8796(2) 1341(2) 4026(1) 23(1)
N(4) 6352(2) 3253(2) 3876(1) 24(1)
N(5) 5803(2) 2386(2) 3463(1) 24(1)
P(1) 7640(1) 714(1) 6585(1) 39(1)
F(1) 8133(2) -16(2) 6667(1) 68(1)
F(2) 7822(3) 672(3) 6008(2) 95(1)
F(3) 7154(2) 1459(2) 6499(2) 76(1)
F(4) 7443(3) 766(2) 7137(1) 82(1)
F(5) 6709(2) 316(2) 6512(1) 66(1)
F(6) 8566(2) 1119(2) 6650(1) 75(1)
C(37) 8132(7) 2392(8) 5635(4) 181(7)
O(1) 7501(8) 2714(4) 6007(3) 195(5)
____________________________________________________________________

14S
Table s7. Bond lengths [Å] and angles [°] for 4a[PF6].
_____________________________________________________
C(1)-N(5) 1.377(4)
C(1)-N(4) 1.377(4)
C(1)-Ir(1) 1.989(3)
C(2)-C(3) 1.336(5)
C(2)-N(5) 1.391(4)
C(2)-H(2) 0.9500
C(3)-N(4) 1.395(5)
C(3)-H(3) 0.9500
C(4)-C(9) 1.393(5)
C(4)-C(5) 1.401(5)
C(4)-N(4) 1.434(4)
C(5)-C(6) 1.405(5)
C(5)-C(10) 1.494(5)
C(6)-C(7) 1.387(6)
C(6)-H(6) 0.9500
C(7)-C(8) 1.393(6)
C(7)-C(11) 1.518(5)
C(8)-C(9) 1.401(5)
C(8)-H(8) 0.9500
C(9)-C(12) 1.503(5)
C(10)-H(10A) 0.9800
C(10)-H(10B) 0.9800
C(10)-H(10C) 0.9800
C(11)-H(11A) 0.9800
C(11)-H(11B) 0.9800
C(11)-H(11C) 0.9800
C(12)-H(12A) 0.9800
C(12)-H(12B) 0.9800
C(12)-H(12C) 0.9800
C(13)-C(18) 1.393(5)
C(13)-C(14) 1.397(5)
C(13)-N(5) 1.442(4)
C(14)-C(15) 1.390(5)

15S
C(14)-C(19) 1.501(5)
C(15)-C(16) 1.394(5)
C(15)-H(15) 0.9500
C(16)-C(17) 1.383(6)
C(16)-C(20) 1.513(5)
C(17)-C(18) 1.390(5)
C(17)-H(17) 0.9500
C(18)-C(21) 1.509(5)
C(19)-H(19A) 0.9800
C(19)-H(19B) 0.9800
C(19)-H(19C) 0.9800
C(20)-H(20A) 0.9800
C(20)-H(20B) 0.9800
C(20)-H(20C) 0.9800
C(21)-H(21A) 0.9800
C(21)-H(21B) 0.9800
C(21)-H(21C) 0.9800
C(22)-N(1) 1.344(5)
C(22)-C(23) 1.381(5)
C(22)-H(22) 0.9500
C(23)-C(24) 1.380(6)
C(23)-H(23) 0.9500
C(24)-C(25) 1.372(6)
C(24)-H(24) 0.9500
C(25)-C(26) 1.381(5)
C(25)-H(25) 0.9500
C(26)-N(1) 1.348(4)
C(26)-H(26) 0.9500
C(27)-N(2) 1.357(5)
C(27)-C(28) 1.372(6)
C(27)-H(27) 0.9500
C(28)-C(29) 1.372(7)
C(28)-H(28) 0.9500
C(29)-C(30) 1.376(7)
C(29)-H(29) 0.9500
C(30)-C(31) 1.389(5)

16S
C(30)-H(30) 0.9500
C(31)-N(2) 1.335(5)
C(31)-H(31) 0.9500
C(32)-N(3) 1.336(5)
C(32)-C(33) 1.388(5)
C(32)-H(32) 0.9500
C(33)-C(34) 1.383(6)
C(33)-H(33) 0.9500
C(34)-C(35) 1.381(6)
C(34)-H(34) 0.9500
C(35)-C(36) 1.387(5)
C(35)-H(35) 0.9500
C(36)-N(3) 1.349(5)
C(36)-H(36) 0.9500
Ir(1)-N(3) 2.129(3)
Ir(1)-N(2) 2.192(3)
Ir(1)-N(1) 2.220(3)
Ir(1)-H(1A) 1.40(4)
Ir(1)-H(2A) 1.49(4)
P(1)-F(4) 1.540(4)
P(1)-F(6) 1.570(3)
P(1)-F(5) 1.572(3)
P(1)-F(1) 1.576(3)
P(1)-F(3) 1.597(3)
P(1)-F(2) 1.600(4)
C(37)-O(1) 1.502(16)
C(37)-H(37A) 0.9800
C(37)-H(37B) 0.9800
C(37)-H(37C) 0.9800
O(1)-H(1) 0.8400

N(5)-C(1)-N(4) 102.6(3)
N(5)-C(1)-Ir(1) 128.4(2)
N(4)-C(1)-Ir(1) 129.0(2)
C(3)-C(2)-N(5) 107.1(3)
C(3)-C(2)-H(2) 126.4

17S
N(5)-C(2)-H(2) 126.4
C(2)-C(3)-N(4) 106.8(3)
C(2)-C(3)-H(3) 126.6
N(4)-C(3)-H(3) 126.6
C(9)-C(4)-C(5) 123.1(3)
C(9)-C(4)-N(4) 119.1(3)
C(5)-C(4)-N(4) 117.7(3)
C(4)-C(5)-C(6) 116.8(3)
C(4)-C(5)-C(10) 121.7(3)
C(6)-C(5)-C(10) 121.5(3)
C(7)-C(6)-C(5) 121.9(4)
C(7)-C(6)-H(6) 119.1
C(5)-C(6)-H(6) 119.1
C(6)-C(7)-C(8) 119.3(4)
C(6)-C(7)-C(11) 119.9(4)
C(8)-C(7)-C(11) 120.8(4)
C(7)-C(8)-C(9) 121.2(4)
C(7)-C(8)-H(8) 119.4
C(9)-C(8)-H(8) 119.4
C(4)-C(9)-C(8) 117.7(3)
C(4)-C(9)-C(12) 121.3(3)
C(8)-C(9)-C(12) 121.0(4)
C(5)-C(10)-H(10A) 109.5
C(5)-C(10)-H(10B) 109.5
H(10A)-C(10)-H(10B) 109.5
C(5)-C(10)-H(10C) 109.5
H(10A)-C(10)-H(10C) 109.5
H(10B)-C(10)-H(10C) 109.5
C(7)-C(11)-H(11A) 109.5
C(7)-C(11)-H(11B) 109.5
H(11A)-C(11)-H(11B) 109.5
C(7)-C(11)-H(11C) 109.5
H(11A)-C(11)-H(11C) 109.5
H(11B)-C(11)-H(11C) 109.5
C(9)-C(12)-H(12A) 109.5
C(9)-C(12)-H(12B) 109.5

18S
H(12A)-C(12)-H(12B) 109.5
C(9)-C(12)-H(12C) 109.5
H(12A)-C(12)-H(12C) 109.5
H(12B)-C(12)-H(12C) 109.5
C(18)-C(13)-C(14) 122.1(3)
C(18)-C(13)-N(5) 119.2(3)
C(14)-C(13)-N(5) 118.5(3)
C(15)-C(14)-C(13) 117.6(3)
C(15)-C(14)-C(19) 120.8(3)
C(13)-C(14)-C(19) 121.6(3)
C(14)-C(15)-C(16) 122.1(4)
C(14)-C(15)-H(15) 118.9
C(16)-C(15)-H(15) 118.9
C(17)-C(16)-C(15) 117.9(3)
C(17)-C(16)-C(20) 121.0(4)
C(15)-C(16)-C(20) 121.0(4)
C(16)-C(17)-C(18) 122.5(3)
C(16)-C(17)-H(17) 118.7
C(18)-C(17)-H(17) 118.7
C(17)-C(18)-C(13) 117.5(3)
C(17)-C(18)-C(21) 120.5(3)
C(13)-C(18)-C(21) 121.9(4)
C(14)-C(19)-H(19A) 109.5
C(14)-C(19)-H(19B) 109.5
H(19A)-C(19)-H(19B) 109.5
C(14)-C(19)-H(19C) 109.5
H(19A)-C(19)-H(19C) 109.5
H(19B)-C(19)-H(19C) 109.5
C(16)-C(20)-H(20A) 109.5
C(16)-C(20)-H(20B) 109.5
H(20A)-C(20)-H(20B) 109.5
C(16)-C(20)-H(20C) 109.5
H(20A)-C(20)-H(20C) 109.5
H(20B)-C(20)-H(20C) 109.5
C(18)-C(21)-H(21A) 109.5
C(18)-C(21)-H(21B) 109.5

19S
H(21A)-C(21)-H(21B) 109.5
C(18)-C(21)-H(21C) 109.5
H(21A)-C(21)-H(21C) 109.5
H(21B)-C(21)-H(21C) 109.5
N(1)-C(22)-C(23) 123.6(4)
N(1)-C(22)-H(22) 118.2
C(23)-C(22)-H(22) 118.2
C(24)-C(23)-C(22) 119.2(4)
C(24)-C(23)-H(23) 120.4
C(22)-C(23)-H(23) 120.4
C(25)-C(24)-C(23) 117.8(4)
C(25)-C(24)-H(24) 121.1
C(23)-C(24)-H(24) 121.1
C(24)-C(25)-C(26) 120.2(4)
C(24)-C(25)-H(25) 119.9
C(26)-C(25)-H(25) 119.9
N(1)-C(26)-C(25) 122.7(4)
N(1)-C(26)-H(26) 118.6
C(25)-C(26)-H(26) 118.6
N(2)-C(27)-C(28) 123.0(4)
N(2)-C(27)-H(27) 118.5
C(28)-C(27)-H(27) 118.5
C(29)-C(28)-C(27) 119.6(4)
C(29)-C(28)-H(28) 120.2
C(27)-C(28)-H(28) 120.2
C(28)-C(29)-C(30) 118.4(4)
C(28)-C(29)-H(29) 120.8
C(30)-C(29)-H(29) 120.8
C(29)-C(30)-C(31) 119.2(4)
C(29)-C(30)-H(30) 120.4
C(31)-C(30)-H(30) 120.4
N(2)-C(31)-C(30) 123.1(4)
N(2)-C(31)-H(31) 118.4
C(30)-C(31)-H(31) 118.4
N(3)-C(32)-C(33) 122.6(4)
N(3)-C(32)-H(32) 118.7

20S
C(33)-C(32)-H(32) 118.7
C(34)-C(33)-C(32) 119.5(4)
C(34)-C(33)-H(33) 120.3
C(32)-C(33)-H(33) 120.3
C(35)-C(34)-C(33) 118.5(4)
C(35)-C(34)-H(34) 120.7
C(33)-C(34)-H(34) 120.7
C(34)-C(35)-C(36) 118.6(4)
C(34)-C(35)-H(35) 120.7
C(36)-C(35)-H(35) 120.7
N(3)-C(36)-C(35) 123.4(4)
N(3)-C(36)-H(36) 118.3
C(35)-C(36)-H(36) 118.3
C(1)-Ir(1)-N(3) 173.55(12)
C(1)-Ir(1)-N(2) 93.89(12)
N(3)-Ir(1)-N(2) 89.14(11)
C(1)-Ir(1)-N(1) 102.17(12)
N(3)-Ir(1)-N(1) 83.10(11)
N(2)-Ir(1)-N(1) 96.80(11)
C(1)-Ir(1)-H(1A) 88.4(16)
N(3)-Ir(1)-H(1A) 88.1(16)
N(2)-Ir(1)-H(1A) 174.8(15)
N(1)-Ir(1)-H(1A) 87.2(15)
C(1)-Ir(1)-H(2A) 89.7(16)
N(3)-Ir(1)-H(2A) 84.9(16)
N(2)-Ir(1)-H(2A) 85.6(15)
N(1)-Ir(1)-H(2A) 167.7(16)
H(1A)-Ir(1)-H(2A) 90(2)
C(22)-N(1)-C(26) 116.4(3)
C(22)-N(1)-Ir(1) 124.9(2)
C(26)-N(1)-Ir(1) 117.0(2)
C(31)-N(2)-C(27) 116.7(3)
C(31)-N(2)-Ir(1) 125.5(3)
C(27)-N(2)-Ir(1) 117.5(3)
C(32)-N(3)-C(36) 117.3(3)
C(32)-N(3)-Ir(1) 120.1(2)

21S
C(36)-N(3)-Ir(1) 122.6(2)
C(1)-N(4)-C(3) 111.7(3)
C(1)-N(4)-C(4) 126.3(3)
C(3)-N(4)-C(4) 121.8(3)
C(1)-N(5)-C(2) 111.7(3)
C(1)-N(5)-C(13) 126.8(3)
C(2)-N(5)-C(13) 121.4(3)
F(4)-P(1)-F(6) 91.1(2)
F(4)-P(1)-F(5) 89.6(2)
F(6)-P(1)-F(5) 179.1(2)
F(4)-P(1)-F(1) 90.2(2)
F(6)-P(1)-F(1) 90.82(18)
F(5)-P(1)-F(1) 89.84(17)
F(4)-P(1)-F(3) 90.1(2)
F(6)-P(1)-F(3) 88.36(17)
F(5)-P(1)-F(3) 90.98(17)
F(1)-P(1)-F(3) 179.1(2)
F(4)-P(1)-F(2) 178.5(3)
F(6)-P(1)-F(2) 89.5(2)
F(5)-P(1)-F(2) 89.8(2)
F(1)-P(1)-F(2) 91.2(2)
F(3)-P(1)-F(2) 88.5(2)
O(1)-C(37)-H(37A) 109.5
O(1)-C(37)-H(37B) 109.5
H(37A)-C(37)-H(37B) 109.5
O(1)-C(37)-H(37C) 109.5
H(37A)-C(37)-H(37C) 109.5
H(37B)-C(37)-H(37C) 109.5
C(37)-O(1)-H(1) 109.5
_____________________________________________________________
Symmetry transformations used to generate equivalent atoms:

22S
Table s8. Anisotropic displacement parameters (Å2x 103) for 4a[PF6]. The
anisotropic displacement factor exponent takes the form: -2π2[ h2 a*2U11 + ... + 2 h k
a* b* U12 ]
_____________________________________________________________________
U11 U22 U33 U23 U13 U12
_____________________________________________________________________
C(1) 20(2) 22(2) 23(2) 2(1) -1(1) -1(1)
C(2) 22(2) 30(2) 40(2) 1(2) -7(2) 5(1)
C(3) 23(2) 28(2) 45(2) 2(2) -4(2) 8(2)
C(4) 22(2) 20(2) 30(2) -3(1) -3(1) 3(1)
C(5) 24(2) 23(2) 29(2) 2(1) -4(1) 0(1)
C(6) 25(2) 22(2) 39(2) -3(2) -2(2) 2(1)
C(7) 26(2) 30(2) 37(2) -10(2) -4(2) 4(2)
C(8) 32(2) 33(2) 31(2) -7(2) -1(2) 6(2)
C(9) 25(2) 29(2) 32(2) -2(2) 2(2) 2(1)
C(10) 38(2) 25(2) 29(2) 1(2) 0(2) 0(2)
C(11) 39(2) 42(2) 45(2) -12(2) -10(2) -2(2)
C(12) 36(2) 40(2) 34(2) -1(2) 9(2) -5(2)
C(13) 17(2) 25(2) 29(2) -4(1) -1(1) 0(1)
C(14) 19(2) 28(2) 25(2) 1(1) -1(1) -2(1)
C(15) 22(2) 28(2) 33(2) -2(2) 0(1) -3(1)
C(16) 22(2) 35(2) 34(2) -10(2) -3(2) -4(2)
C(17) 22(2) 46(2) 24(2) -4(2) -4(1) 0(2)
C(18) 19(2) 39(2) 27(2) 3(2) -5(1) -2(2)
C(19) 27(2) 31(2) 30(2) 0(2) 3(2) -2(2)
C(20) 40(2) 41(2) 45(3) -15(2) -1(2) -5(2)
C(21) 28(2) 48(2) 35(2) 11(2) -5(2) -3(2)
C(22) 26(2) 31(2) 28(2) -1(1) -2(1) -6(2)
C(23) 32(2) 31(2) 38(2) -5(2) 4(2) -9(2)
C(24) 26(2) 36(2) 46(2) -10(2) -8(2) -7(2)
C(25) 31(2) 38(2) 33(2) -11(2) -9(2) 2(2)
C(26) 28(2) 30(2) 25(2) -4(2) -3(1) 1(2)
C(27) 27(2) 32(2) 40(2) -12(2) -5(2) 3(2)
C(28) 33(2) 52(3) 49(3) -27(2) -9(2) 8(2)
C(29) 28(2) 79(3) 31(2) -19(2) -2(2) 7(2)
C(30) 21(2) 68(3) 28(2) 2(2) -1(2) -4(2)

23S
C(31) 20(2) 37(2) 26(2) -2(2) -2(1) -2(2)
C(32) 27(2) 27(2) 39(2) 6(2) -5(2) -4(2)
C(33) 34(2) 29(2) 49(2) 13(2) -11(2) -2(2)
C(34) 34(2) 27(2) 45(2) -4(2) -14(2) 10(2)
C(35) 28(2) 42(2) 31(2) -4(2) -3(2) 12(2)
C(36) 27(2) 34(2) 25(2) 2(2) 1(2) 8(2)
Ir(1) 16(1) 19(1) 21(1) 1(1) -1(1) 0(1)
N(1) 18(1) 21(1) 28(2) -2(1) -4(1) 2(1)
N(2) 19(1) 28(2) 25(2) -4(1) -2(1) -4(1)
N(3) 23(1) 21(1) 26(1) 0(1) -5(1) 2(1)
N(4) 20(1) 21(1) 31(2) 0(1) -4(1) 2(1)
N(5) 19(1) 22(1) 32(2) -1(1) -4(1) 0(1)
P(1) 23(1) 37(1) 56(1) 12(1) 0(1) -1(1)
F(1) 45(2) 50(2) 107(3) 6(2) -3(2) 13(1)
F(2) 106(3) 123(4) 56(2) 8(2) 9(2) -19(3)
F(3) 58(2) 41(2) 129(3) 20(2) -16(2) 7(1)
F(4) 101(3) 76(2) 69(2) -17(2) 10(2) -16(2)
F(5) 40(2) 50(2) 107(3) 13(2) -9(2) -4(1)
F(6) 33(2) 75(2) 117(3) 38(2) -16(2) -18(2)
C(37) 153(10) 288(16) 101(7) 119(10) -63(7) -129(11)
O(1) 422(16) 103(5) 61(3) 30(4) -56(6) -95(7)
___________________________________________________________________

24S
Table s9. Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 10
3) for 4a[PF6].
____________________________________________________________________
x y z U(eq)
____________________________________________________________________

H(2) 4559 2892 3317 37

H(3) 5182 3886 3795 39
H(6) 8361 4985 4123 34
H(8) 7320 4047 5327 38
H(10A) 7648 3841 3259 46
H(10B) 7912 4655 3324 46
H(10C) 6863 4425 3298 46
H(11A) 9158 4949 5042 63
H(11B) 8348 4995 5433 63
H(11C) 8403 5556 4996 63
H(12A) 5546 3246 4837 55
H(12B) 6251 3119 5275 55
H(12C) 6302 2640 4793 55
H(15) 5074 100 3481 33
H(17) 5604 961 2166 36
H(19A) 5785 1343 4224 44
H(19B) 4975 779 4192 44
H(19C) 4767 1601 4115 44
H(20A) 5163 -231 2187 63
H(20B) 4607 -491 2658 63
H(20C) 5685 -616 2627 63
H(21A) 5196 2524 2340 55
H(21B) 6079 2179 2092 55
H(21C) 6183 2659 2571 55
H(22) 9089 3046 3263 34
H(23) 10404 3682 3414 41
H(24) 10852 3897 4227 43
H(25) 9928 3465 4857 41
H(26) 8628 2829 4675 33

25S
H(27) 8087 791 3167 39
H(28) 8241 472 2357 53
H(29) 8232 1340 1749 55
H(30) 8056 2523 1984 47
H(31) 7873 2799 2806 33
H(32) 8134 829 4547 37
H(33) 9263 8 4725 45
H(34) 10663 59 4310 42
H(35) 10895 966 3736 40
H(36) 9701 1730 3559 34
H(1A) 7510(30) 2081(19) 4347(15) 21(10)
H(2A) 7140(30) 1360(20) 3826(14) 30(11)
H(37A) 8636 2719 5569 271
H(37B) 7797 2302 5331 271
H(37C) 8376 1947 5762 271
H(1) 7314 2398 6198 293
____________________________________________________________________

26S
Table s10. Torsion angles [°] for 4a[PF6].
________________________________________________________________
N(5)-C(2)-C(3)-N(4) 0.4(4)
C(9)-C(4)-C(5)-C(6) 1.9(5)
N(4)-C(4)-C(5)-C(6) 178.8(3)
C(9)-C(4)-C(5)-C(10) -175.6(3)
N(4)-C(4)-C(5)-C(10) 1.4(5)
C(4)-C(5)-C(6)-C(7) -0.2(5)
C(10)-C(5)-C(6)-C(7) 177.2(3)
C(5)-C(6)-C(7)-C(8) -1.1(6)
C(5)-C(6)-C(7)-C(11) 179.5(4)
C(6)-C(7)-C(8)-C(9) 0.9(6)
C(11)-C(7)-C(8)-C(9) -179.7(4)
C(5)-C(4)-C(9)-C(8) -2.0(5)
N(4)-C(4)-C(9)-C(8) -178.9(3)
C(5)-C(4)-C(9)-C(12) 176.3(4)
N(4)-C(4)-C(9)-C(12) -0.6(5)
C(7)-C(8)-C(9)-C(4) 0.6(5)
C(7)-C(8)-C(9)-C(12) -177.8(4)
C(18)-C(13)-C(14)-C(15) 6.1(5)
N(5)-C(13)-C(14)-C(15) -178.7(3)
C(18)-C(13)-C(14)-C(19) -171.7(3)
N(5)-C(13)-C(14)-C(19) 3.5(5)
C(13)-C(14)-C(15)-C(16) -1.1(5)
C(19)-C(14)-C(15)-C(16) 176.7(3)
C(14)-C(15)-C(16)-C(17) -2.9(5)
C(14)-C(15)-C(16)-C(20) -179.4(4)
C(15)-C(16)-C(17)-C(18) 2.1(6)
C(20)-C(16)-C(17)-C(18) 178.6(4)
C(16)-C(17)-C(18)-C(13) 2.6(5)
C(16)-C(17)-C(18)-C(21) -172.6(4)
C(14)-C(13)-C(18)-C(17) -6.8(5)
N(5)-C(13)-C(18)-C(17) 178.0(3)
C(14)-C(13)-C(18)-C(21) 168.4(3)
N(5)-C(13)-C(18)-C(21) -6.8(5)

27S
N(1)-C(22)-C(23)-C(24) -0.6(6)
C(22)-C(23)-C(24)-C(25) -0.5(6)
C(23)-C(24)-C(25)-C(26) 0.7(6)
C(24)-C(25)-C(26)-N(1) 0.3(6)
N(2)-C(27)-C(28)-C(29) 0.7(6)
C(27)-C(28)-C(29)-C(30) -0.3(6)
C(28)-C(29)-C(30)-C(31) -0.5(6)
C(29)-C(30)-C(31)-N(2) 0.9(6)
N(3)-C(32)-C(33)-C(34) 1.9(6)
C(32)-C(33)-C(34)-C(35) 1.0(6)
C(33)-C(34)-C(35)-C(36) -2.4(6)
C(34)-C(35)-C(36)-N(3) 1.3(6)
N(5)-C(1)-Ir(1)-N(2) 56.9(3)
N(4)-C(1)-Ir(1)-N(2) -126.4(3)
N(5)-C(1)-Ir(1)-N(1) 154.8(3)
N(4)-C(1)-Ir(1)-N(1) -28.5(3)
C(23)-C(22)-N(1)-C(26) 1.6(5)
C(23)-C(22)-N(1)-Ir(1) -163.3(3)
C(25)-C(26)-N(1)-C(22) -1.4(5)
C(25)-C(26)-N(1)-Ir(1) 164.7(3)
C(1)-Ir(1)-N(1)-C(22) -92.0(3)
N(3)-Ir(1)-N(1)-C(22) 91.8(3)
N(2)-Ir(1)-N(1)-C(22) 3.5(3)
C(1)-Ir(1)-N(1)-C(26) 103.2(3)
N(3)-Ir(1)-N(1)-C(26) -73.0(3)
N(2)-Ir(1)-N(1)-C(26) -161.3(3)
C(30)-C(31)-N(2)-C(27) -0.5(5)
C(30)-C(31)-N(2)-Ir(1) -174.5(3)
C(28)-C(27)-N(2)-C(31) -0.3(5)
C(28)-C(27)-N(2)-Ir(1) 174.3(3)
C(1)-Ir(1)-N(2)-C(31) 47.7(3)
N(3)-Ir(1)-N(2)-C(31) -138.0(3)
N(1)-Ir(1)-N(2)-C(31) -55.0(3)
C(1)-Ir(1)-N(2)-C(27) -126.3(3)
N(3)-Ir(1)-N(2)-C(27) 48.0(3)
N(1)-Ir(1)-N(2)-C(27) 131.0(3)

28S
C(33)-C(32)-N(3)-C(36) -3.1(6)
C(33)-C(32)-N(3)-Ir(1) 176.0(3)
C(35)-C(36)-N(3)-C(32) 1.5(6)
C(35)-C(36)-N(3)-Ir(1) -177.6(3)
N(2)-Ir(1)-N(3)-C(32) -133.5(3)
N(1)-Ir(1)-N(3)-C(32) 129.5(3)
N(2)-Ir(1)-N(3)-C(36) 45.5(3)
N(1)-Ir(1)-N(3)-C(36) -51.4(3)
N(5)-C(1)-N(4)-C(3) 0.3(4)
Ir(1)-C(1)-N(4)-C(3) -177.0(3)
N(5)-C(1)-N(4)-C(4) 176.5(3)
Ir(1)-C(1)-N(4)-C(4) -0.8(5)
C(2)-C(3)-N(4)-C(1) -0.5(4)
C(2)-C(3)-N(4)-C(4) -176.9(3)
C(9)-C(4)-N(4)-C(1) -87.1(4)
C(5)-C(4)-N(4)-C(1) 95.8(4)
C(9)-C(4)-N(4)-C(3) 88.8(4)
C(5)-C(4)-N(4)-C(3) -88.3(4)
N(4)-C(1)-N(5)-C(2) 0.0(4)
Ir(1)-C(1)-N(5)-C(2) 177.3(3)
N(4)-C(1)-N(5)-C(13) -177.6(3)
Ir(1)-C(1)-N(5)-C(13) -0.2(5)
C(3)-C(2)-N(5)-C(1) -0.2(5)
C(3)-C(2)-N(5)-C(13) 177.4(3)
C(18)-C(13)-N(5)-C(1) -105.7(4)
C(14)-C(13)-N(5)-C(1) 79.0(4)
C(18)-C(13)-N(5)-C(2) 77.0(4)
C(14)-C(13)-N(5)-C(2) -98.3(4)
________________________________________________________________
Symmetry transformations used to generate equivalent atoms:

29S
Table s11. Hydrogen bonds for 4a[PF6] [Å and °].
_____________________________________________________________________
D-H...A d(D-H) d(H...A) d(D...A) <(DHA)
____________________________________________________________________
O(1)-H(1)...F(3) 0.84 1.97 2.779(7) 160.0
_____________________________________________________________________
Symmetry transformations used to generate equivalent atoms:

11. DFT Calculations

A series of Density functional theory (DFT) calculations were performed using the the
GAUSSIAN 03i and TURBOMOLE 5.10 suites of programsii to describe the most
energetically favorable path from reactants to products. Preliminary geometry
optimizations were performed on the reactant dihydride complex, Ir(H)2(IMes)(py)3,
using three different levels of theory, (RI-)BP86/SV(P), BP86/lanl2dz and (RI-
)PBE0/def2-TZVP. All three methodologies yielded structures closely resembling the
experimental X-ray structure but the closest match was achieved using (RI-)PBE0/def2-
TZVP, with BP86/lanl2dz a very close second. As a result, given the very considerable
computational economy savings associated with BP86/lanl2dz compared with (RI-
)PBE0/def2-TZVP, it was decided to use the former as the basis of the geometry
optimizations and vibrational frequency calculations performed for the species involved
in each subsequent step of the reaction. These calculations were followed by single point
calculations performed using the TPSSTPSS functional combined with the aug-cc-pVDZ
basis set. The objective of these higher level single point calculations was to obtain more
reliable energies.
The vibrational frequency calculations allowed for the characterization of stationary
points including transition state structures, as well as for the calculation of zero-point
energies, chemical potentials, enthalpies and Gibbs energies at 298.15 K. For each step
of the reaction, changes in enthalpy, ∆H, and Gibbs free energy, ∆G, were computed to
determine the most energetically likely outcome of a particular step. The different

30S
possible reaction paths involved geometry optimizations of the following species
involved in ligand exchange:

[Ir(H)2(IMes)(py)3]+ (labelled R1 in Figure 2)

[Ir(H)2(IMes)(py)2]…py+ Transition State (labelled TS45 in Figure 2)
[Ir(H)2(IMes)(py)2]+ (labelled I5 in Figure 2)
[Ir(H)2(IMes)(Py)2]…(H2)+ Transition State (labelled TS56 in Figure 2)
[Ir(H)2(η2-H2)(IMes)(Py)2]+ (labelled P6 in Figure 2)

Alternative routes considered and shown to be less energetically favourable involved

explicit methanol solvation:

[Ir(H)2(IMes)(Py)2(CH3OH)]+
[Ir(IMes)(Py)2(CH3OH)]+

or loss of H2 directly from the reactant [Ir(H)2(IMes)(py)3]+ or from the pyridine loss
product [Ir(H)2(IMes)(py)2]+.

[Ir(IMes)(py)3]+
[Ir(IMes)(py)2]+

12. Cartesian Coordinates, total electronic energies + zero point energies,

enthalpies and free energies

Cartesian Coordinates, total electronic energies + zero

point energies, enthalpies and free energies

[Ir(H)2(IMes)(py)3]+ Ground State BP86/lanl2dz

Ir -0.148112000 0.546491000 -0.395475000

C -0.546554000 5.238395000 -1.982246000
C -0.864321000 4.138192000 -2.815018000
C -0.741577000 2.829323000 -2.313931000
N -0.319055000 2.565301000 -1.026681000
C -0.018595000 3.640694000 -0.219696000
C -0.117548000 4.975409000 -0.661387000
H -0.631959000 6.265236000 -2.351440000
H -1.202939000 4.285321000 -3.844855000
H -0.972691000 1.952235000 -2.920042000
H 0.310012000 3.406118000 0.794817000
H 0.139171000 5.787375000 0.025653000

31S
C -2.539683000 1.616966000 3.892987000
C -2.942777000 2.181663000 2.659453000
C -2.237728000 1.854519000 1.484348000
N -1.156574000 0.999975000 1.477578000
C -0.788505000 0.434587000 2.678999000
C -1.444961000 0.720654000 3.892526000
H -3.067921000 1.858130000 4.820937000
H -3.796088000 2.863815000 2.598844000
H -2.533571000 2.252858000 0.511774000
H 0.041111000 -0.275416000 2.632849000
H -1.103448000 0.240613000 4.814889000
H -1.592855000 0.300206000 -1.024327000
H 0.480691000 0.228847000 -1.844418000
C -0.893428000 -3.647199000 0.064747000
C 0.478146000 -3.684233000 0.123481000
H -1.630961000 -4.443465000 0.098568000
H 1.168983000 -4.516915000 0.217819000
C -0.138628000 -1.438741000 -0.096111000
N -1.267892000 -2.291950000 -0.071816000
N 0.933198000 -2.347736000 0.025338000
C -2.669538000 -1.938427000 -0.275011000
C -3.549250000 -1.893834000 0.838943000
C -3.146592000 -1.783586000 -1.612310000
C -4.918649000 -1.603556000 0.597235000
C -4.518494000 -1.499675000 -1.799786000
C -5.421878000 -1.393462000 -0.707945000
H -5.606235000 -1.560076000 1.452020000
H -4.896366000 -1.373680000 -2.822818000
C 2.364248000 -2.084842000 -0.056675000
C 2.985438000 -2.131648000 -1.339728000
C 3.125830000 -1.957841000 1.137029000
C 4.393731000 -1.998689000 -1.402779000
C 4.534339000 -1.833052000 1.020845000
C 5.188201000 -1.851088000 -0.235467000
H 4.883707000 -2.036659000 -2.384388000
H 5.132561000 -1.738658000 1.936475000
C -3.091382000 -2.206972000 2.255547000
H -2.004866000 -2.075890000 2.382778000
H -3.608171000 -1.562913000 2.988966000
H -3.330479000 -3.256194000 2.519422000
C -2.219459000 -1.938471000 -2.805870000
H -2.775151000 -1.823922000 -3.752163000
H -1.412415000 -1.182944000 -2.776711000
H -1.735187000 -2.933945000 -2.816495000
C -6.892819000 -1.087124000 -0.946859000
H -7.465123000 -1.078442000 -0.003283000
H -7.024006000 -0.100852000 -1.431794000

32S
H -7.354525000 -1.838835000 -1.614625000
C 2.481315000 -1.953401000 2.514554000
H 3.165081000 -2.380097000 3.268937000
H 2.252988000 -0.916953000 2.834406000
H 1.540880000 -2.530629000 2.538729000
C 2.174191000 -2.344442000 -2.607484000
H 1.410106000 -1.554742000 -2.733383000
H 2.827134000 -2.343581000 -3.496798000
H 1.636219000 -3.311506000 -2.585668000
C 6.704104000 -1.770114000 -0.330497000
H 7.027932000 -1.244108000 -1.246519000
H 7.140957000 -1.249191000 0.539723000
H 7.150066000 -2.783499000 -0.363809000
C 4.417163000 2.306719000 0.895085000
C 4.142646000 1.798919000 -0.395924000
C 2.884670000 1.223286000 -0.662495000
N 1.889641000 1.132190000 0.284324000
C 2.166894000 1.631582000 1.536413000
C 3.404000000 2.215756000 1.877321000
H 4.888692000 1.843729000 -1.194797000
H 2.633131000 0.826948000 -1.647229000
H 1.363782000 1.565530000 2.274716000
H 3.559630000 2.594136000 2.892649000
H 5.386246000 2.760123000 1.127183000

Sum of electronic and zero-point Energies = -1774.072062

a.u.
Sum of electronic and thermal Enthalpies = -1774.028452 a.u.
Sum of electronic and thermal Free Energies = -1774.150544
a.u.

[Ir(H)2(IMes)(py)2]…py+ Transition State Ground State

BP86/lanl2dz

Ir -0.282859000 0.348508000 -0.589795000

N 0.140309000 2.254131000 -1.396200000
C -0.349222000 2.594998000 -2.639967000
C -0.113539000 3.852860000 -3.224160000
C 0.657827000 4.811859000 -2.524419000
C 1.170603000 4.462749000 -1.254006000
C 0.895575000 3.187949000 -0.720983000
H -0.925978000 1.821858000 -3.151006000
H -0.527501000 4.069022000 -4.213458000
H 0.856358000 5.796784000 -2.958784000
H 1.780596000 5.163042000 -0.675716000
H 1.294547000 2.873468000 0.246406000
N 3.124510000 1.319529000 0.984546000

33S
C 3.662539000 0.879158000 -0.197660000
C 5.016404000 1.081279000 -0.551950000
C 5.865689000 1.761591000 0.353244000
C 5.328198000 2.212404000 1.583077000
C 3.960653000 1.973153000 1.853127000
H 2.979486000 0.347768000 -0.870925000
H 5.388679000 0.712479000 -1.512868000
H 6.918683000 1.936680000 0.107550000
H 5.948313000 2.739790000 2.315060000
H 3.510488000 2.314842000 2.793048000
N -0.889036000 1.323228000 1.245268000
C -2.137737000 1.887361000 1.367619000
C -2.542226000 2.575265000 2.529258000
C -1.643919000 2.688598000 3.616603000
C -0.356145000 2.115091000 3.490819000
C -0.007524000 1.450627000 2.297570000
H -2.805535000 1.766221000 0.511717000
H -3.545679000 3.009001000 2.573131000
H -1.936558000 3.212540000 4.532339000
H 0.375070000 2.182796000 4.302237000
H 0.996259000 1.040358000 2.129827000
H 0.193045000 -0.281104000 -1.997573000
H -1.697696000 0.409897000 -1.220338000
C -0.698774000 -1.529927000 -0.052022000
N -1.958801000 -2.127891000 0.123140000
C -1.841413000 -3.510397000 0.393680000
C -0.497603000 -3.806284000 0.396171000
N 0.190034000 -2.601802000 0.122164000
H -2.711751000 -4.140590000 0.550671000
H 0.028490000 -4.742030000 0.560423000
C 1.642628000 -2.554583000 0.017019000
C 2.250284000 -2.828393000 -1.241607000
C 3.666497000 -2.888201000 -1.293009000
C 4.468557000 -2.708467000 -0.137711000
C 3.821017000 -2.450901000 1.098572000
C 2.411546000 -2.378905000 1.203477000
H 4.149462000 -3.102987000 -2.254719000
H 4.426004000 -2.316661000 2.004454000
C 1.420431000 -3.081697000 -2.489217000
C 5.984104000 -2.810428000 -0.210148000
C 1.746868000 -2.168753000 2.554871000
H 0.739683000 -3.944179000 -2.356632000
H 0.791353000 -2.205152000 -2.731654000
H 2.068543000 -3.294093000 -3.356154000
H 6.335224000 -2.939476000 -1.248458000
H 6.352610000 -3.673117000 0.377188000
H 6.467584000 -1.906278000 0.205726000

34S
H 1.307595000 -3.111578000 2.935444000
H 2.479601000 -1.818958000 3.301721000
H 0.925437000 -1.432635000 2.500505000
C -3.251205000 -1.464077000 0.034727000
C -3.901416000 -1.067959000 1.236033000
C -5.180373000 -0.463248000 1.130909000
C -5.815474000 -0.265179000 -0.121288000
C -5.140404000 -0.696260000 -1.294151000
C -3.865985000 -1.311855000 -1.242522000
H -5.694910000 -0.153413000 2.049594000
H -5.625598000 -0.567962000 -2.270402000
C -3.267461000 -1.304295000 2.597884000
C -7.199297000 0.360353000 -0.209828000
C -3.198000000 -1.824222000 -2.509152000
H -2.206831000 -0.995683000 2.615742000
H -3.294288000 -2.376557000 2.872571000
H -3.805220000 -0.747563000 3.383845000
H -7.492311000 0.840262000 0.739972000
H -7.963840000 -0.405607000 -0.443927000
H -7.249541000 1.121961000 -1.009547000
H -3.790796000 -1.558034000 -3.400622000
H -3.098503000 -2.926750000 -2.489070000
H -2.179768000 -1.411428000 -2.630697000

Sum of electronic and zero-point Energies = -1774.049763

a.u.
Sum of electronic and thermal Enthalpies = -1774.00542 a.u.
Sum of electronic and thermal Free Energies = -1774.133342
a.u.

[Ir(H)2(IMes)(py)2]+ Ground State BP86/lanl2dz

Ir -0.054512000 0.612888000 -0.415649000

C 0.418685000 5.388682000 -1.609256000
C -0.779587000 4.686243000 -1.882616000
C -0.894878000 3.337015000 -1.500542000
N 0.122513000 2.663754000 -0.856735000
C 1.284296000 3.354829000 -0.586549000
C 1.465757000 4.702704000 -0.950454000
H 0.533230000 6.436780000 -1.902718000
H -1.617645000 5.171043000 -2.391785000
H -1.793307000 2.752537000 -1.708377000
H 2.072618000 2.797439000 -0.072096000
H 2.412283000 5.199269000 -0.717622000
C 1.228046000 1.923222000 4.247048000
C -0.073006000 2.167987000 3.746347000
C -0.404882000 1.739103000 2.445807000

35S
N 0.491318000 1.079614000 1.633944000
C 1.754910000 0.839902000 2.127814000
C 2.153416000 1.247209000 3.417069000
H 1.511376000 2.248600000 5.252997000
H -0.825208000 2.685341000 4.349293000
H -1.396389000 1.912735000 2.020330000
H 2.439103000 0.299290000 1.465913000
H 3.170826000 1.033456000 3.758022000
H -1.590021000 0.708697000 -0.206300000
H -0.469612000 0.401919000 -1.958007000
C -1.085031000 -3.521613000 -0.243646000
C 0.284771000 -3.631651000 -0.344263000
H -1.859625000 -4.281851000 -0.206090000
H 0.926357000 -4.504490000 -0.420316000
C -0.227610000 -1.364217000 -0.262359000
N -1.389128000 -2.141945000 -0.192089000
N 0.801283000 -2.315035000 -0.349832000
C -2.748002000 -1.630281000 -0.071694000
C -3.289877000 -1.426419000 1.228277000
C -3.510132000 -1.406642000 -1.253540000
C -4.625969000 -0.964008000 1.325117000
C -4.840655000 -0.944658000 -1.102706000
C -5.418696000 -0.720133000 0.174189000
H -5.060018000 -0.803711000 2.320288000
H -5.442393000 -0.765359000 -2.002903000
C 2.219593000 -1.994882000 -0.418254000
C 2.787746000 -1.581421000 -1.660084000
C 3.017094000 -2.176902000 0.749917000
C 4.175380000 -1.291879000 -1.688173000
C 4.400755000 -1.879176000 0.665072000
C 4.999703000 -1.433251000 -0.541733000
H 4.626078000 -0.971535000 -2.636111000
H 5.026421000 -2.015145000 1.556655000
C -2.469758000 -1.703389000 2.478520000
H -1.543496000 -1.099103000 2.495650000
H -3.049130000 -1.472356000 3.388342000
H -2.162603000 -2.765055000 2.536265000
C -2.922149000 -1.655528000 -2.632427000
H -3.647569000 -1.397541000 -3.422268000
H -2.008867000 -1.051348000 -2.788313000
H -2.637671000 -2.716194000 -2.769750000
C -6.863379000 -0.262409000 0.302833000
H -7.056926000 0.208615000 1.282339000
H -7.131614000 0.462511000 -0.486704000
H -7.557422000 -1.120101000 0.206023000
C 2.422073000 -2.696026000 2.050842000
H 2.278885000 -3.793188000 2.015659000

36S
H 3.090993000 -2.482547000 2.902169000
H 1.433417000 -2.250826000 2.262438000
C 1.958053000 -1.495860000 -2.931757000
H 1.171343000 -0.721978000 -2.855605000
H 2.596504000 -1.255942000 -3.798519000
H 1.446697000 -2.454696000 -3.140194000
C 6.493184000 -1.158009000 -0.618688000
H 6.718316000 -0.321503000 -1.303953000
H 6.916420000 -0.916473000 0.372025000
H 7.035111000 -2.045681000 -0.999520000

Sum of electronic and zero-point Energies = -1525.886333

a.u.
Sum of electronic and thermal Enthalpies = -1525.847629 a.u.
Sum of electronic and thermal Free Energies = -1525.961315
a.u.

[Ir(H)2(IMes)(Py)2]…(H2)+ Transition State Ground State

BP86/lanl2dz

Ir -0.040920000 0.613179000 -0.448176000

C 0.207260000 1.981024000 4.362227000
C -0.998915000 2.093032000 3.630400000
C -1.036017000 1.662868000 2.288801000
N 0.063566000 1.127787000 1.654105000
C 1.235210000 1.018220000 2.372273000
C 1.340911000 1.434066000 3.714716000
H 0.262642000 2.309845000 5.404755000
H -1.902930000 2.508058000 4.085932000
H -1.945899000 1.732527000 1.687745000
H 2.088619000 0.585275000 1.841170000
H 2.296359000 1.328563000 4.237319000
H -1.590026000 0.507539000 -0.486244000
H -0.132614000 0.335745000 -2.032527000
C -0.658159000 -3.599240000 -0.181585000
C 0.718144000 -3.583449000 -0.224381000
H -1.360802000 -4.426531000 -0.147285000
H 1.441303000 -4.393518000 -0.238343000
C -0.001343000 -1.370609000 -0.250235000
N -1.089080000 -2.253001000 -0.194964000
N 1.111575000 -2.225327000 -0.261436000
C -2.494377000 -1.873014000 -0.143491000
C -3.119806000 -1.736555000 1.127696000
C -3.213277000 -1.711524000 -1.362186000
C -4.495912000 -1.399883000 1.156813000
C -4.586823000 -1.374580000 -1.278795000
C -5.247546000 -1.216036000 -0.032709000

37S
H -4.993872000 -1.291864000 2.128889000
H -5.155604000 -1.244234000 -2.208333000
C 2.502732000 -1.796747000 -0.293801000
C 3.106323000 -1.476614000 -1.545699000
C 3.248853000 -1.805228000 0.921123000
C 4.473005000 -1.101882000 -1.543119000
C 4.611839000 -1.417594000 0.868537000
C 5.242691000 -1.061158000 -0.351025000
H 4.951789000 -0.852346000 -2.498433000
H 5.198017000 -1.417212000 1.796530000
C -2.345623000 -1.958068000 2.417825000
H -1.449945000 -1.311538000 2.470151000
H -2.977207000 -1.745083000 3.296820000
H -1.992893000 -3.003571000 2.504358000
C -2.535114000 -1.899462000 -2.709110000
H -2.155229000 -2.931777000 -2.831781000
H -3.238186000 -1.700145000 -3.535305000
H -1.668414000 -1.220595000 -2.815925000
C -6.732450000 -0.892447000 0.023824000
H -7.009641000 -0.412445000 0.978688000
H -7.033555000 -0.220411000 -0.799564000
H -7.339006000 -1.814568000 -0.069349000
C 2.634610000 -2.270476000 2.234028000
H 3.235077000 -1.926919000 3.094157000
H 1.597579000 -1.913897000 2.364681000
H 2.599718000 -3.376072000 2.282619000
C 2.331047000 -1.562584000 -2.850140000
H 1.508110000 -0.824118000 -2.879410000
H 2.993476000 -1.376779000 -3.712128000
H 1.873068000 -2.561219000 -2.981223000
C 6.716462000 -0.689219000 -0.389963000
H 6.918207000 0.095164000 -1.141020000
H 7.072773000 -0.327522000 0.590329000
H 7.334610000 -1.567176000 -0.661654000
C -0.272000000 5.422059000 -1.639931000
C 0.538803000 4.997332000 -0.562094000
C 0.579044000 3.630665000 -0.224709000
N -0.136699000 2.673478000 -0.912183000
C -0.926390000 3.095297000 -1.963257000
C -1.016595000 4.446269000 -2.344821000
H 1.134979000 5.709553000 0.015964000
H 1.189961000 3.273895000 0.607563000
H -1.472019000 2.309509000 -2.488180000
H -1.658788000 4.721094000 -3.186644000
H -0.321628000 6.478158000 -1.922759000
H 3.303067000 1.438117000 -0.858562000
H 3.064653000 2.144373000 -0.745380000

38S
Sum of electronic and zero-point Energies = -1527.046568
a.u.
Sum of electronic and thermal Enthalpie s= -1527.005467 a.u.
Sum of electronic and thermal Free Energies = -1527.124048
a.u.

η2-H2)(IMes)(Py)2]+ Ground State BP86/lanl2dz

[Ir(H)2(η

Ir 0.102006000 0.672735000 -0.430224000

C -1.760898000 1.767046000 4.111069000
C -2.589533000 1.671118000 2.968895000
C -2.021416000 1.321968000 1.727190000
N -0.676170000 1.070235000 1.574131000
C 0.124618000 1.161045000 2.691726000
C -0.378735000 1.502878000 3.962837000
H -2.177895000 2.038632000 5.086009000
H -3.664873000 1.862666000 3.029057000
H -2.629541000 1.229702000 0.825616000
H 1.186396000 0.951754000 2.541031000
H 0.306056000 1.561258000 4.814134000
H -1.386291000 0.371094000 -0.894412000
H 0.455198000 0.454102000 -1.988570000
C -0.149774000 -3.595713000 -0.201299000
C 1.217298000 -3.460042000 -0.124835000
H -0.780298000 -4.479476000 -0.221067000
H 2.007544000 -4.202258000 -0.065053000
C 0.315685000 -1.315383000 -0.232499000
N -0.692172000 -2.292460000 -0.264862000
N 1.495509000 -2.074909000 -0.142371000
C -2.130475000 -2.070256000 -0.344827000
C -2.891533000 -2.076477000 0.856500000
C -2.740015000 -1.944625000 -1.625844000
C -4.295756000 -1.904701000 0.753083000
C -4.144988000 -1.775991000 -1.675289000
C -4.941696000 -1.752365000 -0.500067000
H -4.897479000 -1.907726000 1.671045000
H -4.629931000 -1.673017000 -2.654547000
C 2.856047000 -1.562204000 -0.062212000
C 3.568459000 -1.297905000 -1.267001000
C 3.451735000 -1.395700000 1.218924000
C 4.893272000 -0.809183000 -1.156610000
C 4.779797000 -0.901019000 1.275298000
C 5.516902000 -0.600513000 0.101820000
H 5.454629000 -0.595138000 -2.075013000
H 5.252042000 -0.763195000 2.256446000
C -2.236624000 -2.291010000 2.212527000

39S
H -1.339099000 -1.659233000 2.339323000
H -2.941050000 -2.062979000 3.030332000
H -1.910976000 -3.341658000 2.339409000
C -1.915351000 -1.991013000 -2.900974000
H -1.363515000 -2.945854000 -2.993779000
H -2.559345000 -1.887015000 -3.790468000
H -1.163762000 -1.179624000 -2.917102000
C -6.452926000 -1.604171000 -0.590470000
H -6.893743000 -1.312278000 0.378609000
H -6.742476000 -0.847395000 -1.342051000
H -6.924745000 -2.559130000 -0.893587000
C 2.716929000 -1.769433000 2.498240000
H 3.173778000 -1.276663000 3.374189000
H 1.645687000 -1.502536000 2.460000000
H 2.765434000 -2.861262000 2.677490000
C 2.940224000 -1.540530000 -2.629483000
H 2.025599000 -0.933535000 -2.762861000
H 3.644924000 -1.284682000 -3.438384000
H 2.648446000 -2.600332000 -2.757376000
C 6.951962000 -0.103880000 0.183779000
H 7.160931000 0.663368000 -0.583238000
H 7.178822000 0.328644000 1.173712000
H 7.664842000 -0.934583000 0.015178000
C -0.602085000 5.460398000 -1.546281000
C 0.191771000 5.097188000 -0.433584000
C 0.366944000 3.733589000 -0.127653000
N -0.204189000 2.727755000 -0.873942000
C -0.980408000 3.086559000 -1.954598000
C -1.196298000 4.430688000 -2.313212000
H 0.674916000 5.853820000 0.191482000
H 0.974876000 3.418620000 0.723788000
H -1.412825000 2.261453000 -2.522678000
H -1.818704000 4.657790000 -3.183608000
H -0.751142000 6.512408000 -1.808757000
H 1.903829000 0.947292000 -0.520079000
H 1.769642000 1.059843000 0.311448000

Sum of electronic and zero-point Energies = -1527.056918

a.u.
Sum of electronic and thermal Enthalpies = -1527.017809 a.u.
Sum of electronic and thermal Free Energies = -1527.131818
a.u.

[Ir(H)2(IMes)(Py)2(CH3OH)]+ Ground State BP86/lanl2dz

Ir -0.030893000 0.642681000 -0.409290000

C -0.762294000 5.395427000 -1.596430000

40S
C -1.067975000 4.351542000 -2.502686000
C -0.859303000 3.014619000 -2.117437000
N -0.363122000 2.670486000 -0.876948000
C -0.075261000 3.690059000 0.001636000
C -0.258575000 5.048936000 -0.321772000
H -0.912664000 6.443080000 -1.875339000
H -1.460759000 4.564044000 -3.501382000
H -1.072145000 2.179732000 -2.786861000
H 0.307207000 3.386546000 0.977753000
H -0.009138000 5.815446000 0.418134000
C -2.059574000 1.482436000 4.093990000
C -2.785420000 1.720768000 2.902950000
C -2.181710000 1.452537000 1.657910000
N -0.899504000 0.962065000 1.547783000
C -0.202894000 0.722126000 2.711442000
C -0.743758000 0.970630000 3.988461000
H -2.505714000 1.683850000 5.073088000
H -3.808754000 2.106969000 2.929447000
H -2.710809000 1.611784000 0.715761000
H 0.801786000 0.313119000 2.582902000
H -0.143552000 0.761056000 4.879344000
H -1.443135000 0.298884000 -0.997905000
H 0.552652000 0.494771000 -1.906408000
C -0.262978000 -3.627132000 -0.323958000
C 1.105274000 -3.504016000 -0.277529000
H -0.898639000 -4.506285000 -0.371663000
H 1.890726000 -4.254095000 -0.275457000
C 0.213476000 -1.339061000 -0.258874000
N -0.798900000 -2.320398000 -0.310128000
N 1.392333000 -2.118952000 -0.236046000
C -2.236941000 -2.093620000 -0.386653000
C -3.007881000 -2.138949000 0.806738000
C -2.839373000 -1.930074000 -1.667592000
C -4.411202000 -1.961918000 0.698911000
C -4.243443000 -1.759281000 -1.722376000
C -5.048119000 -1.768365000 -0.552346000
H -5.018864000 -1.990588000 1.612527000
H -4.721240000 -1.626105000 -2.701630000
C 2.763610000 -1.640892000 -0.167460000
C 3.443568000 -1.287569000 -1.373347000
C 3.434264000 -1.658838000 1.090322000
C 4.794279000 -0.863250000 -1.272377000
C 4.791115000 -1.244982000 1.133312000
C 5.487799000 -0.836757000 -0.032509000
H 5.325550000 -0.580036000 -2.189768000
H 5.317598000 -1.256881000 2.096372000
C -2.366520000 -2.401986000 2.160153000

41S
H -1.456227000 -1.794349000 2.306247000
H -3.070261000 -2.177152000 2.979587000
H -2.066783000 -3.463241000 2.262608000
C -2.006299000 -1.942407000 -2.938651000
H -2.642087000 -1.789869000 -3.827189000
H -1.238093000 -1.146878000 -2.916147000
H -1.474414000 -2.904892000 -3.065614000
C -6.557785000 -1.606715000 -0.648250000
H -7.009534000 -1.401622000 0.337847000
H -6.834071000 -0.781943000 -1.330574000
H -7.029879000 -2.526710000 -1.044424000
C 2.743305000 -2.141364000 2.357135000
H 2.816810000 -3.242570000 2.448904000
H 3.216265000 -1.710430000 3.257145000
H 1.667109000 -1.895982000 2.364499000
C 2.771053000 -1.408170000 -2.730350000
H 1.838760000 -0.816904000 -2.775096000
H 3.443066000 -1.063791000 -3.534321000
H 2.499759000 -2.460136000 -2.942672000
C 6.951346000 -0.429290000 0.028984000
H 7.175413000 0.393171000 -0.673592000
H 7.244641000 -0.106699000 1.043140000
H 7.604615000 -1.279712000 -0.247575000
O 2.139413000 1.355747000 0.214178000
H 2.757467000 0.788129000 -0.313563000
C 2.823437000 1.913126000 1.399384000
H 2.069067000 2.471774000 1.973128000
H 3.622458000 2.604548000 1.077073000
H 3.252303000 1.109743000 2.026563000

Sum of electronic and zero-point Energies = -1641.563947

a.u.
Sum of electronic and thermal Enthalpie s= -1641.521453 a.u.
Sum of electronic and thermal Free Energies = -1641.641606
a.u.

[Ir(IMes)(Py)2(CH3OH)]+ Ground State BP86/lanl2dz

Ir 0.153412000 0.723816000 -0.080501000

C -0.473467000 5.575790000 -0.683828000
C -0.168462000 4.728196000 -1.777443000
C 0.020340000 3.351210000 -1.557661000
N -0.080386000 2.780549000 -0.300469000
C -0.375505000 3.613681000 0.762993000
C -0.574668000 4.998714000 0.604442000
H -0.625190000 6.649548000 -0.831469000

42S
H -0.079673000 5.123937000 -2.793711000
H 0.261491000 2.660322000 -2.369165000
H -0.435636000 3.135195000 1.743231000
H -0.801664000 5.609780000 1.483313000
C -3.816274000 0.937087000 2.679853000
C -3.835181000 1.385920000 1.337998000
C -2.687088000 1.251511000 0.538545000
N -1.511606000 0.692772000 1.016784000
C -1.505812000 0.234499000 2.324390000
C -2.624657000 0.349348000 3.167786000
H -4.697897000 1.037848000 3.320400000
H -4.732125000 1.835300000 0.901711000
H -2.667277000 1.571256000 -0.504507000
H -0.566976000 -0.206223000 2.662817000
H -2.552569000 -0.018349000 4.196008000
C -0.139405000 -3.548547000 -0.173522000
C 1.217938000 -3.434882000 -0.000807000
H -0.768557000 -4.425387000 -0.293121000
H 1.992840000 -4.191401000 0.079724000
C 0.337498000 -1.259645000 -0.035944000
N -0.673360000 -2.238910000 -0.200889000
N 1.508744000 -2.051721000 0.078299000
C -2.087339000 -2.018323000 -0.480799000
C -3.053219000 -2.439745000 0.477243000
C -2.473957000 -1.497572000 -1.751452000
C -4.425739000 -2.278243000 0.157361000
C -3.857001000 -1.352035000 -2.017606000
C -4.850747000 -1.736631000 -1.080123000
H -5.177201000 -2.594658000 0.892481000
H -4.165698000 -0.951181000 -2.991878000
C 2.879519000 -1.579283000 0.193584000
C 3.747938000 -1.731030000 -0.932143000
C 3.358670000 -1.082092000 1.441775000
C 5.107021000 -1.344929000 -0.785818000
C 4.724948000 -0.721506000 1.536375000
C 5.618838000 -0.849310000 0.439433000
H 5.781133000 -1.456304000 -1.644613000
H 5.103782000 -0.344142000 2.494849000
C -2.665661000 -3.078938000 1.803445000
H -1.689081000 -2.721856000 2.172619000
H -3.426512000 -2.865671000 2.574203000
H -2.597219000 -4.180982000 1.711942000
C -1.448155000 -1.117497000 -2.803792000
H -1.939896000 -0.809145000 -3.742232000
H -0.815338000 -0.281498000 -2.434020000
H -0.770999000 -1.963037000 -3.033928000
C -6.329107000 -1.611760000 -1.415895000

43S
H -6.947487000 -1.511209000 -0.506399000
H -6.527397000 -0.740908000 -2.066166000
H -6.686639000 -2.509758000 -1.957052000
C 2.429384000 -0.925485000 2.630429000
H 1.882983000 -1.863281000 2.844652000
H 2.985833000 -0.633030000 3.536632000
H 1.673524000 -0.144551000 2.405769000
C 3.268839000 -2.322516000 -2.255433000
H 2.214381000 -2.078183000 -2.480454000
H 3.896401000 -1.969829000 -3.092136000
H 3.336180000 -3.427220000 -2.242413000
C 7.089141000 -0.492494000 0.588681000
H 7.568922000 -0.317739000 -0.389847000
H 7.228178000 0.412109000 1.207598000
H 7.642251000 -1.313357000 1.085352000
O 1.964468000 0.972421000 -1.243237000
H 2.381132000 0.087808000 -1.422195000
C 3.036118000 1.881182000 -0.718038000
H 2.561090000 2.856202000 -0.555567000
H 3.824250000 1.959468000 -1.485480000
H 3.435942000 1.480036000 0.227273000

Sum of electronic and zero-point Energies = -1640.370072

a.u.
Sum of electronic and thermal Enthalpies = -1640.328890 a.u.
Sum of electronic and thermal Free Energies = -1640.444447
a.u.

[Ir(IMes)(py)3]+ Ground State BP86/lanl2dz

Ir 0.000018000 0.663420000 0.000001000

C 0.000019000 5.611466000 -0.000044000
C 0.207973000 4.885124000 -1.197120000
C 0.202110000 3.477784000 -1.164514000
N 0.000042000 2.761970000 0.000014000
C -0.202037000 3.477825000 1.164514000
C -0.207922000 4.885169000 1.197061000
H 0.000010000 6.705934000 -0.000067000
H 0.370397000 5.397102000 -2.150412000
H 0.350039000 2.883602000 -2.069113000
H -0.349963000 2.883679000 2.069136000
H -0.370354000 5.397185000 2.150331000
C -4.159551000 1.183835000 2.513249000
C -4.036380000 1.655369000 1.184477000
C -2.843886000 1.431989000 0.474430000
N -1.763939000 0.765721000 1.026109000
C -1.896690000 0.292948000 2.318238000

44S
C -3.064588000 0.488295000 3.078170000
H -5.076820000 1.350036000 3.086816000
H -4.854828000 2.189224000 0.692641000
H -2.713899000 1.768777000 -0.555654000
H -1.030738000 -0.235591000 2.719335000
H -3.105331000 0.099515000 4.100336000
C -0.667524000 -3.569849000 -0.159223000
C 0.667686000 -3.569860000 0.158105000
H -1.355696000 -4.390700000 -0.335988000
H 1.355921000 -4.390716000 0.334599000
C 0.000009000 -1.332834000 -0.000185000
N -1.076780000 -2.218687000 -0.253378000
N 1.076850000 -2.218701000 0.252720000
C -2.460941000 -1.891860000 -0.579852000
C -3.483583000 -2.272947000 0.338275000
C -2.779815000 -1.314107000 -1.843265000
C -4.833216000 -2.029884000 -0.022487000
C -4.143202000 -1.089388000 -2.153437000
C -5.188019000 -1.444240000 -1.262278000
H -5.624637000 -2.316559000 0.682314000
H -4.394618000 -0.646299000 -3.125879000
C 2.460927000 -1.891887000 0.579569000
C 3.483816000 -2.272596000 -0.338391000
C 2.779443000 -1.314438000 1.843256000
C 4.833378000 -2.029525000 0.022810000
C 4.142691000 -1.089755000 2.153858000
C 5.187801000 -1.444286000 1.262852000
H 5.624991000 -2.315895000 -0.681895000
H 4.393841000 -0.646951000 3.126503000
C -3.180310000 -2.945381000 1.670279000
H -2.213825000 -2.621174000 2.092360000
H -3.972721000 -2.721600000 2.405440000
H -3.136332000 -4.047198000 1.566035000
C -1.701762000 -0.930662000 -2.838333000
H -2.140728000 -0.624266000 -3.803137000
H -1.109227000 -0.086754000 -2.421802000
H -1.002707000 -1.768599000 -3.025334000
C -6.645655000 -1.239252000 -1.645038000
H -7.285579000 -1.100160000 -0.755643000
H -6.775537000 -0.362185000 -2.303898000
H -7.035293000 -2.119361000 -2.193366000
C 1.701079000 -0.931312000 2.838114000
H 2.139755000 -0.625116000 3.803114000
H 1.108593000 -0.087351000 2.421618000
H 1.002031000 -1.769342000 3.024718000
C 3.181069000 -2.944625000 -1.670728000
H 2.214037000 -2.621511000 -2.092366000

45S
H 3.972978000 -2.719313000 -2.405971000
H 3.138702000 -4.046570000 -1.567113000
C 6.645248000 -1.239176000 1.646266000
H 7.286733000 -1.107586000 0.756891000
H 6.775695000 -0.357605000 2.299033000
H 7.032468000 -2.115939000 2.201616000
C 4.159663000 1.183658000 -2.513159000
C 3.064650000 0.488245000 -3.078135000
C 1.896718000 0.292966000 -2.318238000
N 1.763977000 0.765701000 -1.026095000
C 2.843977000 1.431833000 -0.474355000
C 4.036508000 1.655136000 -1.184364000
H 3.105379000 0.099508000 -4.100318000
H 1.030739000 -0.235500000 -2.719374000
H 2.714007000 1.768556000 0.555755000
H 4.855002000 2.188882000 -0.692487000
H 5.076966000 1.349790000 -3.086689000

Sum of electronic and zero-point Energies = -1772.894289

a.u.
Sum of electronic and thermal Enthalpies = -1772.851648 a.u.
Sum of electronic and thermal Free Energies = -1772.970577
a.u.

[Ir(IMes)(py)2]+ Ground State BP86/lanl2dz

Ir -0.003064000 -1.021528000 0.079585000

C 4.042001000 -2.057755000 2.549382000
C 3.926613000 -2.341983000 1.167500000
C 2.791973000 -1.906171000 0.461785000
N 1.752072000 -1.229165000 1.079404000
C 1.878833000 -0.938649000 2.426374000
C 2.998806000 -1.336483000 3.178088000
H 4.918074000 -2.385434000 3.117786000
H 4.709989000 -2.885952000 0.632036000
H 2.672552000 -2.077475000 -0.610488000
H 1.043601000 -0.397679000 2.874855000
H 3.041878000 -1.089315000 4.243036000
C 0.670531000 3.089304000 -0.402181000
C -0.673624000 3.113032000 -0.117600000
H 1.363006000 3.893905000 -0.630228000
H -1.367982000 3.943316000 -0.032003000
C -0.001376000 0.886736000 -0.073863000
N 1.086949000 1.738162000 -0.375656000
N -1.088685000 1.776498000 0.083728000
C 2.471712000 1.369471000 -0.642196000

46S
C 3.464821000 1.713122000 0.319418000
C 2.813236000 0.776537000 -1.891687000
C 4.817362000 1.414805000 0.015374000
C 4.177945000 0.498142000 -2.146086000
C 5.197621000 0.812400000 -1.209603000
H 5.590321000 1.669329000 0.751743000
H 4.453028000 0.043754000 -3.106675000
C -2.469879000 1.455984000 0.420001000
C -3.471843000 1.621964000 -0.577876000
C -2.799441000 1.092594000 1.758265000
C -4.820493000 1.372314000 -0.215597000
C -4.159821000 0.853782000 2.067805000
C -5.187747000 0.989533000 1.097610000
H -5.600713000 1.491093000 -0.978409000
H -4.425591000 0.574719000 3.095664000
C 3.117486000 2.396148000 1.634056000
H 2.163262000 2.030778000 2.052879000
H 3.911614000 2.229155000 2.381689000
H 3.015095000 3.491355000 1.506313000
C 1.752968000 0.439456000 -2.924025000
H 2.210199000 0.082454000 -3.862218000
H 1.087031000 -0.354387000 -2.524975000
H 1.118893000 1.315374000 -3.160064000
C 6.659493000 0.543463000 -1.530808000
H 7.273134000 0.476426000 -0.615439000
H 6.786399000 -0.394536000 -2.100816000
H 7.081515000 1.358994000 -2.150061000
C -1.732036000 0.958867000 2.829635000
H -2.184333000 0.801585000 3.823302000
H -1.075300000 0.095595000 2.596253000
H -1.089791000 1.858553000 2.880599000
C -3.145369000 2.076651000 -1.993113000
H -2.141902000 1.751231000 -2.317271000
H -3.886989000 1.682998000 -2.709561000
H -3.170932000 3.181073000 -2.074502000
C -6.644925000 0.768468000 1.472484000
H -7.269721000 0.571639000 0.583884000
H -6.762518000 -0.079316000 2.171449000
H -7.060889000 1.663143000 1.975637000
C -4.039911000 -2.420213000 -2.221503000
C -3.000169000 -1.787792000 -2.944554000
C -1.882097000 -1.284062000 -2.256253000
N -1.753972000 -1.383828000 -0.881819000
C -2.790106000 -1.975215000 -0.176205000
C -3.922590000 -2.510260000 -0.813790000
H -3.044173000 -1.691317000 -4.033529000
H -1.050029000 -0.806347000 -2.776665000

47S
H -2.669850000 -1.997015000 0.909224000
H -4.702913000 -2.979352000 -0.207680000
H -4.914470000 -2.827459000 -2.738446000

Sum of electronic and zero-point Energies = -1524.675656

a.u.
Sum of electronic and thermal Enthalpies = -1524.638119 a.u.
Sum of electronic and thermal Free Energies = -1524.747441
a.u.

i
Gaussian 03, Revision B.03, Frisch, M. J. et al. Gaussian, Inc., Wallingford CT, (2004).
ii
R. Ahlrichs, M. Bär, M. Häser, H. Horn and C. Kölmel, Chem. Phys. Lett. 1989, 162, 165.

48S