Full Paper

Received: 16 May 2013 Revised: 5 August 2013 Accepted: 5 August 2013 Published online in Wiley Online Library: 24 September 2013

(wileyonlinelibrary.com) DOI 10.1002/aoc.3052

Ruthenium(II) complexes of hybrid

8-hydroxyquinoline–thiosemicarbazone
ligands: synthesis, characterization and
catalytic applications
M. Nirmala, R. Manikandan, G. Prakash and P. Viswanathamurthi*

A series of new hexa-coordinated ruthenium(II) hydroxyquinoline–thiosemicarbazone complexes of the type [Ru(CO)(EPh3)(B)

(L)] (E = P or As; B = PPh3, AsPh3 or Py; L = hydroxyquinoline–thiosemicarbazone) were synthesized by reacting ruthenium pre-
cursor complexes [RuHCl(CO)(EPh3)2(B)] (E = P or As; B = PPh3, AsPh3 or Py) with hydroxyquinoline–thiosemicarbazone ligands
in ethanol. The new complexes were characterized by analytical and spectroscopic (FT-IR, UV–visible, NMR (1H, 13C and 31P)
and fast atom bombardment (FAB)–mass spectrometric methods. Based on the spectral results, an octahedral geometry
was assigned for all the complexes. The new complexes showed good catalytic activity for the conversion of aldehydes to
amides in the presence of hydroxylamine hydrochloride–sodium bicarbonate and for the oxidation of alkanes into their cor-
responding alcohols and ketones in the presence of m-chloroperbenzoic acid. The complexes also catalyzed the N-alkylation
of benzylamine in the presence of KOtBu in alcohol medium. Copyright © 2013 John Wiley & Sons, Ltd.
Supporting information may be found in the online version of this article.

Keywords: thiosemicarbazone ligands; ruthenium(II) complexes; aldehyde-to-amide conversion; alkane oxidation; N-alkylation

Introduction for the atom-economical and cost effective synthesis of amides.[10]

Aldehydes are highly desirable starting materials for amide
In Schiff base metal complexes, the environment at the coordina- synthesis because of their availability and non-toxic nature. In
tion center can be modified by attaching different substituents to this context, the coupling of aldehydes with hydroxylamine cat-
the ligand, which provides a useful range of steric and electronic alyzed by metal complexes has been revealed in recent years as
properties essential for the fine-tuning of structure and reactivity.[1] an appealing tool for the generation of primary amides.[11] The
Therefore, Schiff base ligands are among the most fundamental reaction involves the rearrangement of an aldoxime intermedi-
chelating systems particularly for transition metals.[2] Among the ate, generated in situ by the condensation of an aldehyde with
transition metals, ruthenium complexes have attracted much NH2OH, via initial dehydration to the corresponding nitrile,
interest mainly because of their vital applications in several organic followed by hydration of the C¼N bond.[10] Several catalytic
syntheses.[3,4] Ruthenium complexes containing carbonyl and systems, based on ruthenium,[12] iron,[13] iridium,[14] palla-
triphenylphosphine/arsine ligands are fascinating due to their reac- dium,[15] copper,[16] zinc,[17] indium[18] and scandium[19] com-
tivity and efficiency in catalysis.[5,6] They have been used as catalyst pounds, able to promote this catalytic transformation have
precursors for a variety of purposes, including hydrogenation, already been described in the literature.[20] In a recent advance,
oxidation, polymerization, carbon–carbon bond formation and Williams and co-workers reported a ruthenium catalyst for this
aldehyde-to-amide conversion. reaction with high selectivity, excellent yield and low catalyst
Amides are one of the most important and prolific functional loading with p-toluene sulfonic acid as an additive.[21] Further,
groups, with a great importance in both research and industrial Crabtree et al. reported ruthenium terpyridine complexes as an
chemistry owing to their prevalence in detergents, lubricants, efficient catalyst to achieve high yields without any additive.[22]
biologically active compounds and pharmaceuticals.[7] They are In recent years, catalytic oxidation of saturated hydrocarbons
routinely prepared through the union of carboxylic acids and de- under mild conditions has become an exciting and challenging
rivatives (halides, anhydrides or esters) with amines.[8] However, scientific goal and has received increasing attention.[23–28]
these classical methods present several drawbacks, such as the Although iron complexes are considered to be one of the most
use of toxic, corrosive and/or expensive materials, highly exother-
mic reactions, low tolerance to sensitive functional groups, com-
plex reaction conditions and wasteful procedures. New, efficient
and sustainable synthetic routes for this important class of * Correspondence to: P. Viswanathamurthi, Department of Chemistry, Periyar
University, Salem 636011, Tamilnadu, India. E-mail: viswanathamurthi72@
compounds therefore need to be made available.[9] In the search gmail.com
for improved methods, metal-catalyzed transformations have
18

emerged in the last two decades as the most promising alternative Department of Chemistry, Periyar university, Salem, 636011, India

Appl. Organometal. Chem. 2014, 28, 18–26 Copyright © 2013 John Wiley & Sons, Ltd.
Ru(II) complexes of hybrid 8-hydroxyquinoline–thiosemicarbazone ligands

promising catalysts for this industrially important reaction, a obtained at room temperature using tetramethylsilane as internal
variety of metal-based homogeneous catalysts for alkane oxida- standard. 31P NMR spectra of the complexes were obtained at room
tion have been reported by replacing iron with different transi- temperature using o-phosphoric acid as a reference. Electrospray
tion metals such as Mn, Co, Cu, Ru and Os.[29–49] Among them, ionization mass spectra were recorded by liquid chromatogra-
ruthenium has attracted much attention and a few Ru(II/III) com- phy–mass spectrometry quadrupole time-of-flight Micro Analyzer
plexes of tripodal 4N ligands based on tris(2-pyridylmethyl)amine (Shimadzu) at SAIF, Panjab University, Chandigarh. Melting points
(TPA)[50] and tris(benzimidazol-2-ylmethyl)amine (NTB)[51] have were recorded on a Technico micro heating table and are
been studied as catalysts for alkane hydroxylation, and the in- uncorrected. The catalytic yields were determined by gas chroma-
volvement of a Ru(V)¼O intermediate in the catalytic cycle has tography–flame ionization detection (GC-FID) using an ACME
been proposed. Itoh et al. have reported Ni(II) complexes of tripo- 6000 series instrument with a DP-5 column of 30 m length, 0.53
dal phenolate ligands, which are capable of catalyzing the oxida- mm diameter and 5.00 μm film thickness. The precursor complexes
tion of cyclohexane to cyclohexanol using m-chloroperbenzoic [RuHCl(CO)(PPh3)3],[61] [RuHCl(CO)(AsPh3)3],[62] [RuHCl(CO)(Py)
acid (m-CPBA) with up to 100% conversion based on the oxidant (PPh3)2],[63] and ligands[64] L1 and L3 were prepared according
in solvent-free conditions.[52] However, the factors determining to literature procedures.
selectivity as well as efficiency of the catalysts and the nature of
intermediate species still remain unclear.
The N-alkylation of amines is an important transformation for Preparation of 8-Hydroxyquinoline-2-Thiosemicarbazone (L2)
the preparation of pharmaceuticals, agrochemicals, polymers, 2-Formyl-8-hydroxyquinoline[65] (0.173 g; 1 mmol) was dissolved in
dyes and other fine chemicals.[53] Traditionally, the alkylation of dried and degassed ethanol (10 ml) and treated with
amines is achieved using conventional alkylating agents, such thiosemicarbazide (0.0911 g; 1 mmol) in 1:1 molar ratio. A drop of
as alkyl halides. Many alkyl halides have toxic or even mutagenic acetic acid was added, and the reaction was subsequently refluxed
properties and an alternative to such reagents is therefore for 4 h. The light-yellow, crystalline product obtained was isolated
advantageous.[54] In recent years, a number of reports on the in good yield, washed with ether (30 ml) and dried in air. Yield
hydroamination[55] and hydroamino-methylation of olefins or al- 86%; yellow crystalline solid; m.p. 238°C. Anal. Found (%): C 53.52;
kynes[56] for the synthesis of amines have been reported. Com- H 3.98; N 22.58; S 12.96. Calcd for C11H10N4OS (%): C 53.64; H 4.09;
pared to the frequently applied N-alkylations with alkyl halides N 22.75; S 13.02. IR (KBr, cm1): 3389 (C–OH), 3211 (N–H), 1611
and reductive amination methods, an economically and environ- (C¼N), 833 (C¼S). UV λmax (εmax) 351 (16 682), 318 (28 452), 260
mentally attractive method is the N-alkylation of amines using (4520). 1H NMR (DMSO-d6, δ, ppm): 10.78 (s, 1Hk, N–NH–C¼S),
primary and secondary alcohols. Since the early 1980s, transition 10.23 (s, 1He, C–OH), 3.26 (s, 2Hl, NH2), 8.77 (s, 1Hj, N¼CH), 7.38 (d,
metal complexes,[57] particularly ruthenium complexes, have 1Ha, J = 7.4 Hz), 7.23 (d, 1Hb, J = 7.4 Hz), 6.37 (dd, 1Hg, J(Hg–Hf) = 7.2
been shown to be active for this transformation. Recently, Hz, J(Hg–Hh) = 7.2 Hz), 6.34 (dd, 1Hh, J(Hh–Hg) = 7.2 Hz, J(Hh–Hf) = 1.5
Williams, Beller and co-workers[58] were able to obtain good Hz), 6.03 (dd, 1Hf, J(Hf–Hg) = 7.2 Hz, J(Hf–Hh) = 1.5 Hz). 13C NMR
yields in the N-alkylation of indoles by using 0.2–0.5 mol% of (DMSO-d6, δ, ppm): 176.96 (Ck, C¼S), 151.43 (Ce, C–OH), 149.93
the dimeric Shvo ruthenium catalyst (0.4–1 mol% Ru) at 110°C. (Cb, C–C¼N), 140.56 (Cj, CH¼N), 136.52 (Ca), 115.82 (Cd), 110.01
Matute also reported that small loadings of ruthenium pincer (Ci), 134.20 (Ch),129.31 (Cg), 126.84 (Cf),116.58 (Cc). The structure of
complex (1 mol% Ru) afforded excellent results in the selective the ligands used in this study is given in Fig. 1.
alkylation of (hetero-)aromatic amines with alcohols.[59] With this
background, as part of our continuous interest at the design of
novel metal complexes and their catalytic applications to organic General Procedure for Synthesis of New Ruthenium(II)
synthesis, we herein report the synthesis and characterization of a Hydroxyquinoline–Thiosemicarbazone Complexes (1–9)
series of new ruthenium(II) hydroxyquinoline–thiosemicarbazone
complexes along with their catalytic activity towards the conver- All the new metal complexes were synthesized according to the
sion of aldehyde to amide in the presence of NaHCO3, alkane following general procedure. To a solution of [RuHCl(CO)(EPh3)2
oxidation in the presence of oxidizing agent m-chloroperbenzoic (B)] (E = P or As; B = PPh3, AsPh3 or Py) (0.1 g; 0.1 mmol) in ethanol
acid and N-alkylation of amine with alcohols in the presence (20 ml), the appropriate ligand (0.0259–0.0338 g, 0.1 mmol) was
of KOtBu. added in 1:1 molar ratio. The mixture was heated under reflux
for 5 h in a water bath, whereby the solution turned from pale
yellow to reddish-brown. After reducing the content to half vol-
Experimental ume and standing for a day, the complex was obtained as a red-
dish-brown precipitate. It was filtered and washed several times
Materials and Methods with ether and dried under vacuum, and the purity of the com-
All the reagents used were chemically pure and AR grade. The plexes was checked by thin-layer chromatography.
solvents were purified and dried according to standard proce- Elemental composition and properties are as follows.
dures.[60] RuCl3.3H2O was purchased from Loba Chemie Pvt Ltd.
Microanalyses of carbon, hydrogen, nitrogen and sulfur were
h a
carried out using a Vario EL III elemental analyzer at SAIF, Cochin, g i b S
India. IR spectra were recorded as KBr pellets on a Nicolet Avatar c l R
N
model spectrophotometer in the 4000–400 cm1 range. Electronic f
e d N N k N
j H H
spectra were recorded in dichloromethane using a Shimadzu OH
UV-1650 PC spectrophotometer in the 800–200 nm range. 1H, 13C (R= CH3 (L1), R = H (L2), R = C6H5(L3))
and 31P NMR spectra were recorded on a Jeol GSX-400 instrument
19

using DMSO-d6 as solvent. 1H NMR and 13C NMR spectra were Figure 1. General structure of hydroxyquinoline–thiosemicarbazone ligands.

Appl. Organometal. Chem. 2014, 28, 18–26 Copyright © 2013 John Wiley & Sons, Ltd. wileyonlinelibrary.com/journal/aoc
 M. Nirmala et al.

[Ru(CO)(PPh3)2(L1)] (1) AsPh3), 2.95 (d, 3Hm, J = 4.2 Hz, CH3). 13C NMR (DMSO-d6, δ, ppm):
203.54 (Cn, CO), 182.05 (Ck, C–S), 159.30 (Ce, C–O), 147.25 (Ck,
Yield 82%; brown solid; m.p. 125°C. Anal. Found (%): C 64.32; H
C¼N), 145.41 (Cj, N¼CH), 139.56 (Ca), 137.06 (Ch),135.85 (Cg),
4.08; N 5.98; S 3.31. Calcd for C49H40N4O2P2SRu (%): C 64.53; H
132.91 (Cf), 131.85 (Cb), 130.54 (Cc), 130.21 (Cd), 129.24 (Ci), 128.01,
4.42; N 6.14; S 3.52. IR (KBr, cm1): 3354 (N–H), 1981 (CO),
124.20, 121.21, 120.03 (AsPh3), 30.74 (Cm, CH3). MS (FAB),
1380 (C–O), 1574 (C¼N), 760 (C–S). UV λmax (εmax) 432 (1875),
m/z = 1001 [M+].
366 (28 310), 310 (16 892), 261 (11 372). 1H NMR (DMSO-d6, δ,
ppm): 8.37 (s, 1Hj, N¼CH), 8.72 (m, 1Hl, CH3–NH–C–S), 7.23 (d, [Ru(CO)(AsPh3)2(L2)] (5)
1Ha, J = 7.4 Hz), 7.25 (d, 1Hb, J = 7.4 Hz), 7.27 (dd, 1Hg, J(Hg–Hf) = 7.2
Yield 80%; brown solid; m.p. 234°C. Anal. Found (%): C 58.15; H
Hz, J(Hg–Hh) = 7.2 Hz), 7.40 (dd, 1Hf, J(Hf–Hg) = 7.2 Hz, J(Hf–Hh) = 1.5
3.65; N 5.42; S 3.02. Calcd for C48H38N4O2As2SRu (%): C 58.48; H
Hz), 7.43 (dd, 1Hh, J(Hh–Hg) = 7.2 Hz, J(Hh–Hf) = 1.5 Hz), 7.70–7.56
3.89; N 5.68; S 3.25. IR (KBr, cm1): 1975 (CO), 1360 (C–O),
(m, 15H, PPh3), 2.75 (d, 3Hm, J = 4.2 Hz, CH3). 13C NMR (DMSO-d6,
1567 (C¼N), 747 (C–S). UV λmax (εmax): 426 (5732), 358 (12 487),
δ, ppm): 204.26 (Cn, CO), 179.85 (Ck, C–S), 158.21 (Ce, C–O),
261 (11 592), 230 (10 890). 1H NMR (DMSO-d6, δ, ppm): 4.65 (s,
148.32 (Ck, C¼N), 144.78 (Cj, N¼CH), 138.55 (Ca), 136.96
2Hl, NH2), 8.27 (s, 1Hj, N¼CH), 7.17 (d, 1Ha, J = 7.4 Hz), 7.21 (d,
(Ch),137.62 (Cg), 133.55 (Cf), 133.05 (Cb), 130.12 (Cc, tert), 129.74
1Hb, J = 7.4 Hz), 7.26 (dd, 1Hg, J(Hg–Hf) = 7.2 Hz, J(Hg–Hh) = 7.2 Hz),
(Cd), 128.20 (Ci), 128.86, 128.37, 127.89 (PPh3), 30.21 (Cm, CH3).
7.32 (dd, 1Hf, J(Hf–Hg) = 7.2 Hz, J(Hf–Hh) = 1.5 Hz), 7.38 (dd, 1Hh,
31
P NMR (CDCl3, δ, ppm): 46.79 and 48.26 (2s, 2PPh3). MS (FAB),
J(Hh–Hg) = 7.2 Hz, J(Hh–Hf) = 1.5 Hz), 7.86–7.74 (m, 15H, AsPh3).
m/z = 911.5 [M+]. 13
C NMR (DMSO-d6, δ, ppm): 203.94 (Cn, CO), 182.73 (Ck, C–S),
[Ru(CO)(PPh3)2(L2)] (2) 158.59 (Ce, C–O), 149.84 (Ck, C¼N), 145.88 (Cj, N¼CH), 139.15 (Ca),
138.96 (Ch),138.22 (Cg), 134.41 (Cf), 133.28 (Cb), 132.69 (Cc), 131.90
Yield 84%; brown solid; m.p. 278°C. Anal. Found (%): C 64.08; H (Cd), 130.91 (Ci), 129.78, 128.95, 125.91, 121.73, 120.10 (AsPh3).
4.04; N 6.11; S 3.28. Calcd for C48H38N4O2P2SRu (%): C 64.21; H MS (FAB), m/z = 986.2 [M+].
4.27; N 6.24; S 3.57. IR (KBr, cm1): 1963 (CO), 1360 (C–O),
1572 (C¼N), 759 (C–S). UV λmax (εmax) 434 (1232), 358 (22 490), [Ru(CO)(AsPh3)2(L3)] (6)
261 (11 592). 1H NMR (DMSO-d6, δ, ppm): 3.41 (s, 2Hl, NH2), 8.28 Yield 82%; brown solid; m.p. 117°C. Anal. Found (%): C 60.89; H
(s, 1Hj, N¼CH), 7.25 (d, 1Ha, J = 7.4 Hz), 7.28 (d, 1Hb, J = 7.4 Hz), 3.82; N 5.07; S 2.95. Calcd for C54H42N4O2As2SRu (%): C 61.08; H
7.32 (dd, 1Hg, J(Hg–Hf) = 7.2 Hz, J(Hg–Hh) = 7.2 Hz), 7.42 (dd, 1Hf, J 3.99; N 5.28; S 3.02. IR (KBr, cm1): 3368 (N–H), 1973 (CO),
h
(Hf–Hg) = 7.2 Hz, J(Hf–Hh) = 1.5 Hz), 7.48 (dd, 1H , J(Hh–Hg) = 7.2 Hz, J 1376 (C–O), 1578 (C¼N), 737 (C–S). UV λmax (εmax): 441 (1381),
(Hh–Hf) = 1.5 Hz), 7.72–7.65 (m, 15H, PPh 3 ). 13
C NMR (DMSO-d6, δ, 363 (27 890), 278 (14 821), 248 (19 243) . 1H NMR (DMSO-d6, δ,
ppm): 204.87 (Cn, CO), 177.56 (Ck, C–S), 156.21 (Ce, C–O), ppm): 11.11 (s, 1Hl, C–NH–C–S), 8.31 (s, 1Hj, N¼CH), 7.18 (d, 1Ha,
149.23 (Ck, C¼N), 144.87 (Cj, N¼CH), 139.21 (Ca), 137.86 J = 7.4 Hz), 7.24 (d, 1Hb, J = 7.4 Hz), 7.28 (dd, 1Hg, J(Hg–Hf) = 7.2
(Ch),136.26 (Cg), 134.11 (Cf), 131.85 (Cb), 130.74 (Cc), 129.36 (Cd), Hz, J(Hg–Hh) = 7.2 Hz), 7.33 (dd, 1Hf, J(Hf–Hg) = 7.2 Hz, J(Hf–Hh) = 1.5
128.54 (Ci), 128.21, 125.31, 121.85, 120.13 (PPh3). MS (FAB), Hz), 7.39 (dd, 1Hh, J(Hh–Hg) = 7.2 Hz, J(Hh–Hf) = 1.5 Hz), 7.70–7.47
m/z = 898 [M+]. (m, 15H, AsPh3). 13C NMR (DMSO-d6, δ, ppm): 203.74 (Cn, CO),
[Ru(CO)(PPh3)2(L3)] (3) 182.30 (Ck, C–S), 161.2 (Ce, C–O), 149.51 (Ck, C¼N), 145.81 (Cj,
N¼CH), 138.65 (Ca), 136.89 (Ch),135.06 (Cg), 132.57 (Cf), 131.47
Yield 87%; brown solid; m.p. 158°C. Anal. Found (%): C 66.24; H (Cb), 130.89 (Cc), 130.34 (Cd), 128.96 (Ci), 127.52, 126.91, 123.23,
4.12; N 5.62; S 3.09. Calcd for C54H42N4O2P2SRu (%): C 66.59; H 122.05 (AsPh3).
4.35; N 5.75; S 3.29. IR (KBr, cm1): 3368 (N–H), 1981 (CO),
[Ru(CO)(PPh3)(Py)(L1)] (7)
1374 (C–O), 1573 (C¼N), 759 (C–S). UV λmax (εmax) 428 (5687),
374 (22 327), 278 (10 156), 250 (9742). 1H NMR (DMSO-d6, δ, Yield 86%; brown solid; m.p. 105°C. Anal. Found (%): C 59.02; H
ppm): 11.34 (s, 1Hl, C–NH–C–S), 8.39 (s, 1Hj, N¼CH), 7.18 (d, 1Ha, 3.98; N 9.52; S 4.16. Calcd for C36H30N5O2PSRu (%): C 59.33; H
J = 7.4 Hz), 7.21 (d, 1Hb, J = 7.4 Hz), 7.26 (dd, 1Hg, J(Hg–Hf) = 7.2 4.15; N 9.61; S 4.40. IR (KBr, cm1): 3357 (N–H), 1958 (CO),
Hz, J(Hg–Hh) = 7.2 Hz), 7.32 (dd, 1Hf, J(Hf–Hg) = 7.2 Hz, J(Hf–Hh) = 1.5 1390 (C–O), 1542 (C¼N), 750 (C–S). UV λmax (εmax): 450 (9971),
Hz), 7.40 (dd, 1Hh, J(Hh–Hg) = 7.2 Hz, J(Hh–Hf) = 1.5 Hz), 7.71–7.49 371 (24 396), 264 (12 394), 236 (18 391). 1H NMR (DMSO-d6, δ,
(m, 15H, PPh3). 13C NMR (DMSO-d6, δ, ppm): 203.31 (Cn, CO), ppm): 8.21 (s, 1Hj, N–CH), 8.72 (m, 1Hl, CH3–NH–C–S), 7.19 (d,
181.25 (Ck, C–S), 157.95 (Ce, C–O), 147.22 (Ck, C¼N), 145.42 1Ha, J = 7.4 Hz), 7.23 (d, 1Hb, J = 7.4 Hz), 7.32 (dd, 1Hg, J(Hg–Hf) = 7.2
(Cj, N¼CH), 137.81 (Ca), 136.78 (Ch),135.91 (Cg), 134.23 (Cf), Hz, J(Hg–Hh) = 7.2 Hz), 7.38 (dd, 1Hf, J(Hf–Hg) = 7.2 Hz, J(Hf–Hh) = 1.5
133.21 (Cb), 130.29 (Cc), 130.12 (Cd), 129.78 (Ci), 128.94, 128.37, Hz), 7.41 (dd, 1Hh, J(Hh–Hg) = 7.2 Hz, J(Hh–Hf) = 1.5 Hz), 8.04–7.70
124.10 (PPh3). 31P NMR (CDCl3, δ, ppm): 47.41 and 49.19 (2s, (m, 5H, Py), 7.67–7.55 (m, 15H, PPh3), 2.92 (d, 3Hm, J = 4.2 Hz,
2PPh3). MS (FAB), m/z = 975.2 [M+]. CH3). 13C NMR (DMSO-d6, δ, ppm): 205.02 (Cn, CO), 175.23 (Ck,
C–S), 162.14 (Ce, C–O), 149.45 (Ck, C¼N), 144.71 (Cj, N¼CH),
[Ru(CO)(AsPh3)2(L1)] (4)
138.23 (Ca), 137.58 (Ch),137.95 (Cg), 134.53 (Cf), 133.27 (Cb),
Yield 80%; brown solid; m.p. 268°C. Anal. Found (%): C 58.71; H 132.36 (Cc), 131.44 (Cd), 131.20 (Ci), 128.88, 128.68, 128.25 (Py),
3.91; N 5.48; S 3.02. Calcd for C49H40N4O2As2SRu (%): C 58.56; H 127.95, 127.65, 125.68 (PPh3), 29.84 (Cm, CH3). 31P NMR (CDCl3,
4.03; N 5.60; S 3.21. IR (KBr, cm1): 3345 (N–H), 1934 (CO), δ, ppm): 43.25. MS (FAB), m/z = 729.4 [M+].
1367 (C–O), 1595 (C¼N), 745 (C–S). UV λmax (εmax) 430 (5432),
[Ru(CO)(PPh3)(Py)(L2)] (8)
359 (26 890), 270 (11 321), 241 (20 216). 1H NMR (DMSO-d6,
δ, ppm): 8.21(s, 1Hj, N¼CH), 8.79 (m, 1Hl, CH3–NH–C–S), 7.19 Yield 85%; brown solid; m.p. 140°C, Anal. Found (%): C 58.65; H
(d, 1Ha, J = 7.4 Hz), 7.23 (d, 1Hb, J = 7.4 Hz), 7.33 (dd, 1Hg, J(Hg–Hf) = 7.2 3.72; N 9.65; S 4.31. Calcd for C35H28N5O2PSRu (%): C 58.82; H
Hz, J(Hg–Hh) = 7.2 Hz), 7.39 (dd, 1Hf, J(Hf–Hg) = 7.2 Hz, J(Hf–Hh) = 1.5 Hz), 3.95; N 9.80; S 4.49. IR (KBr, cm1): 1938 (CO), 1375 (C–O),
20

7.42 (dd, 1Hh, J(Hh–Hg) = 7.2 Hz, J(Hh–Hf) = 1.5 Hz), 7.87–7.64 (m, 15H, 1553 (C¼N), 745 (C–S). UV λmax (εmax): 419 (2378), 357 (25 376),

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Ru(II) complexes of hybrid 8-hydroxyquinoline–thiosemicarbazone ligands

290 (10 152), 257 (12 891). 1H NMR (DMSO-d6, δ, ppm): 3.75 (s, 2H, and refluxed at 110–150°C for 6 h. On completion of the reac-
NH2), 8.31 (s, 1Hj, N¼CH), 7.12 (d, 1Ha, J = 7.4 Hz), 7.28 (d, 1Hb, tion, brine (3 ml) and CH2Cl2 (5 ml) were added. The organic
J = 7.4 Hz), 7.30 (dd, 1Hg, J(Hg–Hf) = 7.2 Hz, J(Hg–Hh) = 7.2 Hz), 7.34 layer was separated and the aqueous layer was extracted into
(dd, 1Hf, J(Hf–Hg) = 7.2 Hz, J(Hf–Hh) = 1.5 Hz), 7.39 (dd, 1Hh, J(Hh–Hg) = CH2Cl2. The combined organic extracts were dried with mag-
7.2 Hz, J(Hh–Hf) = 1.5 Hz), 8.12–7.68 (m, 5H, Py), 7.55–7.44 (m, 15H, nesium sulfate and concentrated. The compound was purified
PPh3). 13C NMR (DMSO-d6, δ, ppm): 203.41(Cn, CO), 179.54 (Ck, by column chromatography (pentane–diethyl ether, 1:1) using
C–S), 154.89 (Ce, C–O), 147.47 (Ck, C¼N), 144.87 (Cj, N¼CH), silica (200 mesh) as solid phase and characterized by compar-
140.15 (Ca), 138.56 (Ch), 136.26 (Cg), 135.76 (Cf), 132.63 (Cb), ing their 1H NMR spectra with those given in the literature.[67]
131.74 (Cc), 130.26 (Cd), 129.54 (Ci), 129.15, 128.36, 127.65 (Py), Yields were obtained by the 1H NMR integration compared to
126.25, 124.51, 120.78 (PPh3). 1,3,5-trimethoxybenzene as an internal standard.

[Ru(CO)(PPh3)(Py)(L3)] (9)

Yield 80%; brown solid; m.p. 114°C. Anal. Found (%): C 62.01; H Results and Discussion
3.85; N 8.62; S 3.95. Calcd for C41H32N5O2PSRu (%): C 62.27; H
4.08; N 8.86; S 4.05. IR (KBr, cm1): 3378 (N–H), 1916 (CO), Diamagnetic, hexa-coordinated low-spin ruthenium(II) hydroxy-
1367 (C–O), 1541 (C¼N), 750 (C–S). UV λmax (εmax): 440 (1364), quinoline–thiosemicarbazone complexes of the general formula
360 (21 823), 275 (9860), 247 (19 241). 1H NMR (DMSO-d6, δ, [Ru(CO)(EPh3)2(B)(L)] (B = PPh3, AsPh3 or Py; L = hydroxyqu-
ppm): 11.85 (s, 1Hl, C–NH–C–S), 8.65 (s, 1Hj, N¼CH), 7.22 (d, 1Ha, inoline–thiosemicarbazone ligand) were synthesized in quantita-
J = 7.4 Hz), 7.25 (d, 1Hb, J = 7.4 Hz), 7.27 (dd, 1Hg, J(Hg–Hf) = 7.2 Hz, J tive yields from the reaction of [RuHCl(CO)(EPh3)2(B)] (E = P or As;
f
(Hg–Hh) = 7.2 Hz), 7.34 (dd, 1H , J(Hf–Hg) = 7.2 Hz, J(Hf–Hh) = 1.5 Hz),
B = PPh3, AsPh3 or Py) with hydroxyquinoline–thiosemicarbazone
h
7.39 (dd, 1H , J(Hh–Hg) = 7.2 Hz, J(Hh–Hf) = 1.5 Hz), 8.22–7.58 (m, 5H, ligands at 1:1 molar ratio in ethanol medium (Scheme 1). In all
Py), 7.57–7.42 (m, 15H, PPh3). 13C NMR (DMSO-d6, δ, ppm): 205.34 these reactions, it was observed that the hydroxyquinoline–
(Cn, CO), 178.51 (Ck, C–S), 154.52 (Ce, C–O), 149.32 (Ck, C¼N), thiosemicarbazone behaved as dianionic tridentate ligand by
146.45 (Cj, N¼CH), 138.91 (Ca), 137.92 (Ch),136.74 (Cg), 134.25 (Cf), replacing one molecule of triphenylphosphine/arsine, one
132.15 (Cb), 131.10 (Cc), 130.09 (Cd), 129.98 (Ci), 129.72, 128.36, molecule of hydride and one molecule of chloride from the
127.39 (Py), 126.35, 124.53, 119.18 (PPh3). starting complexes.
The analytical data (C, H, N, S) of all the hydroxyquinoline–
thiosemicarbazone ligands and their ruthenium(II) complexes
General Procedure for the Ruthenium-Catalyzed
are in good agreement with the calculated values, thus
Aldehyde-to-Amide Conversion
confirming the proposed mononuclear composition for all the
Catalytic conversion of aldehydes to amides was carried out complexes. Molecular ion peaks (M+) were observed with m/z
using ruthenium(II) complexes as catalysts in the following proce- values 911.5, 898, 975.2, 1001, 986.2 and 729.4, corresponding
dure. The reaction vessel was charged with aldehyde (1 mmol), to complexes 1, 2, 3, 4, 5 and 7 respectively in the FAB mass
NH2OH.HCl (1 mmol), NaHCO3 (1 mmol) and ruthenium catalyst spectra of the complexes, supporting the proposed molecular
(0.5 mmol), and the mixture was placed under an atmosphere formulae (supporting information, Figs S1–S4). All the ligands
of N2. About 2 ml dry and degassed toluene was added and and their complexes are stable at room temperature, non-
the mixture was stirred for 15 min at room temperature, followed hygroscopic, insoluble in water and soluble in common organic
by reflux for 24 h. On completion of the reaction, 2–3 ml metha-
nol was added to the mixture, followed by filtration through h a
g i b
celite to remove the catalyst and NaHCO3. The crude product S
was then purified by column chromatography (MeOH/CH2Cl2, f c N l R
e d N N k N
1:1) using silica (200 mesh) as solid phase, providing the amide j H H
OH
in good yield. The products were characterized by comparing +
their 1H NMR spectra with those given in the literature.[66]
[RuHCl(CO)(EPh3)2(B)]

General Procedure for the Ruthenium-Catalyzed Oxidation

of Alkanes EtOH/ reflux 5h

In a typical reaction, ruthenium(II) complex (0.35 × 103 mmol)

was added to a mixture of alkane (1.75 mmol) and oxidant a h
b i g
m-CPBA (0.35 mol) in CH2Cl2–CH3CN mixture (3:1, v/v) and stirred
c
at room temperature for 48 h. The reaction mixture was filtered j f
nN d e
over a silica column, and was subjected to GC analysis. The CO
formation of product was determined by GC, comparing with N O
N Ru
authentic sample. H C
lN k S EPh3 B
mR
General Procedure for the Ruthenium-Catalyzed N-Alkylation
of Amines (E = P or As; B = PPh3, AsPh3 or Py;
R = CH3, H or C6H5)
A mixture of amine (0.3 mmol), ruthenium(II) complex
(3 × 103 mmol) and KOtBu (0.12 mmol) in alcohol (0.9 mmol) Scheme 1. Synthesis of ruthenium(II) hydroxyquinoline–thiosemicarbazone
21

was placed in a flask under atmospheric pressure of nitrogen complexes.

Appl. Organometal. Chem. 2014, 28, 18–26 Copyright © 2013 John Wiley & Sons, Ltd. wileyonlinelibrary.com/journal/aoc
 M. Nirmala et al.

solvents such as dichloromethane, chloroform, benzene, acetoni- coordination mode is azomethine nitrogen. The terminal methyl
trile, ethanol, methanol, DMSO, etc. However, our efforts to ob- group in ligand L1 and their complexes showed a peak around
tain single crystals of the complexes were unsuccessful. 2.90–3.10 ppm. The terminal NH2 protons in complexes 2, 5, 8 are
seen in the positions around 3.75–3.41 ppm with slight deviations
from that of the ligand spectrum, confirming the non-involvement
Infrared Spectroscopic Analysis
of this group in coordination with metal.[73] The terminal –NHl–R
The IR spectra of free ligands were compared with those of proton appeared in the region 11.87–8.79 ppm in the ligands
new complexes in order to confirm the coordination of ligands L1, L3 and their complexes. The multiplet observed in the
to ruthenium metal. In the spectra of free ligand, a strong 7.22–8.44 ppm range has been assigned to the aromatic protons
band was observed in the region 1630–1611 cm1, which is char- of the hydroxyquinoline–thiosemicarbazones ligands and the
acteristic of the azomethine group, and this band has been phenyl groups of triphenylphosphine/ triphenylarsine/ pyridine.
shifted to a lower frequency (1573–1541 cm1) in complexes,
indicating the coordination of Schiff bases with metal through 13
C NMR Spectroscopic Analysis
the azomethine nitrogen atom.[68] A strong band obtained around
1320–1300 cm1 in the spectra of free ligands was assigned to The 13C NMR spectra of the complexes (supporting information,
phenolic C–O stretching which had been shifted to a higher Figs S5–S8) showed a peak in the 205.34–203.31 ppm region due
frequency (1390–1360 cm1) in the complexes, showing that the to terminal CO carbon. The azomethine (>C¼N) carbon exhibited
other coordination is through the phenolic oxygen atom.[69] This a peak in the region 147.22–149.84 ppm. The peaks observed in
has been further confirmed by the disappearance of the broad the 119.18–139.56 ppm region have been assigned to aromatic
νOH band around 3388–3370 cm1 in all complexes due to binding carbons. The peak appearing in the 154.52–162.14 ppm region
of the phenolic –OH group with ruthenium metal via deproton- can be attributed to the coordinated carbonyl carbon (C–O). A sharp
ation.[70] The medium-intensity band at 870 cm1 and a shoulder singlet appearing at 175.23–182.73 ppm was due to C–S carbon.
at 3210–3260 cm1 was due to the presence of C¼S and NH
groups in the ligands, which disappeared in the complexes, and a 31
P NMR Spectral Analysis
new band appeared for C–S around 750–760 cm1 due to
31
enolization of the ligand, followed by deprotonation prior to the P NMR spectra were recorded for few representative complexes
coordination of the thiolate sulfur.[71] The strong absorption band (1, 3 and 7) in order to confirm the presence of triphenylphosphine
around 1981–1938 cm1 was due to the CO stretching of the group along with heterocyclic nitrogen base and its geometry
terminally coordinated carbonyl group. The complexes in the ruthenium(II) hydroxyquinoline–thiosemicarbazone com-
containing pyridine as coordinated ligand exhibited a peak at plexes. The signals appeared at 46.79–48.26 and 47.41–49.19 ppm
about 1027–1031 cm1 due to aromatic C¼N stretching. in the spectra of 1, 3 and indicated that the two
triphenylphosphine ligands were cis to each other in these
complexes. However, complex 7 exhibited only one signal at
Electronic Spectroscopic Analysis
43.25 ppm, consistent with the presence of one triphenylphosphine
All the ruthenium(II) hydroxyquinoline–thiosemicarbazone com- group. This observation indicated the retention of coordinated
plexes are diamagnetic, indicating the presence of ruthenium in pyridine in the complexes even after the coordination of
+2 oxidation state, corresponding to the electronic configuration thiosemicarbazones. The 31P NMR spectral studies indicated a more
t62g e0g. The electronic spectra of the new complexes have been labile Ru–P bond compared to Ru–N bond in these complexes,
recorded in CH2Cl2 solution in the region 800–200 nm. All the ru- which is a reflection of better σ-donating ability of the nitrogen
thenium(II) complexes displayed three to four bands in the region bases compared to that of phosphorus in triphenylphosphine.[74]
450–240 nm. The bands in the region 450–360 nm have been
assigned to metal-to-ligand charge-transfer transitions. The other
Catalytic Aldehyde-to-Amide Conversion
high-intensity bands appearing around 350–240 nm were probably
due to ligand-centered transitions. The observed electronic spectral The synthesized ruthenium(II) complexes were employed as a
pattern of our complexes was similar to the octahedral ruthenium catalyst for the conversion of aldehydes to their corresponding
complexes of the same type reported earlier.[72] amides. The effects of solvents, base and catalyst/substrate ratio
were investigated using 4-nitrobenzaldehyde as substrate. No
1 considerable reaction was observed in the absence of catalyst
H NMR Spectroscopic Analysis
or base. The optimized time for the reaction was 24 h and the
The 1H NMR spectra of the ligands and corresponding ruthenium(II) catalyst/substrate ratio was 1:100 (Table 1). The conversion of
complexes were recorded in DMSO-d6 to confirm the presence 4-nitobenzaldehyde to 4-nitrobenzamide was performed in dif-
of coordinated ligand in the complexes. The signal around ferent solvent media such as acetonitrile, benzene, chloroform,
10.24 ppm due to the hydrazinic proton (–NH–C¼S) of the free dichloromethane, toluene and xylene. Among these, toluene
hydroxyquinoline–thiosemicarbazone ligands, which disappeared was found to be best, with high conversion (Fig. 2). It was there-
in the complexes, confirmed the thio-enolization. Spectra of free fore used as solvent for the conversion of all substrates. Similarly,
ligands exhibited a peak in the region 9.58–9.54 ppm, which is char- NaHCO3 was selected as base among KHCO3, CH3COONa and
acteristic of the phenolic O–H group. The peak disappeared in the Et3N (Table 2).
corresponding complexes, confirming the binding of ligand with Using the above optimized conditions, the catalytic conversion
metal ion via deprotonation of the phenolic hydroxyl group. The of aldehydes to amides in the presence of NH2OH.HCl and NaHCO3,
azomethine proton of the ligands exhibited a signal in the region using all the synthesized ruthenium(II) hydroxyquinoline–
8.26–8.10 ppm which underwent a downfield shift (8.4–8.3 ppm) thiosemicarbazone complexes as catalysts, has also been investi-
22

in the corresponding complexes. This indicated that the other gated (Table 3). It has been observed that the electron-withdrawing

wileyonlinelibrary.com/journal/aoc Copyright © 2013 John Wiley & Sons, Ltd. Appl. Organometal. Chem. 2014, 28, 18–26
Ru(II) complexes of hybrid 8-hydroxyquinoline–thiosemicarbazone ligands

Table 1. Effect of catalyst:substrate (C:S) ratio on the conversion of Table 3. Catalytic aldehyde-to-amide conversion using ruthenium(II)
4- nitrobenzaldehyde to 4-nitrobenzamide using complex 1 hydroxyquinoline–thiosemicarbazone complexes
Entry C:S ratio Yield (%)a Ru(II) complex
O NaHCO3/ O
1 1:1000 <25
+ reflux 24h
2 1:500 30 R H NH2 OH.HCl R NH2
3 1:400 36
(R = 4-NO2Ph, Ph, 4-MePh)
4 1:300 45
5 1:200 58
6 1:100 86 Complex Substrate Product Yield (%)a
a
Isolated yield after column chromatography (average of two runs). 1 4-Nitrobenzaldehyde 4-Nitrobenzamide 86
Benzaldehyde Benzamide 79
Tolualdehyde Toluamide 81
2 4-Nitrobenzaldehyde 4-Nitrobenzamide 82
Benzaldehyde Benzamide 74
Tolualdehyde Toluamide 76
3 4-Nitrobenzaldehyde 4-Nitrobenzamide 84
Benzaldehyde Benzamide 79
Tolualdehyde Toluamide 84
4 4-Nitrobenzaldehyde 4-Nitrobenzamide 86
Benzaldehyde Benzamide 75
Tolualdehyde Toluamide 83
5 4-Nitrobenzaldehyde 4-Nitrobenzamide 82
Benzaldehyde Benzamide 78
Tolualdehyde Toluamide 78
6 4-Nitrobenzaldehyde 4-Nitrobenzamide 85
Benzaldehyde Benzamide 77
Tolualdehyde Toluamide 81
7 4-Nitrobenzaldehyde 4-Nitrobenzamide 83
Benzaldehyde Benzamide 73
Tolualdehyde Toluamide 78
8 4-Nitrobenzaldehyde 4-Nitrobenzamide 81
Figure 2. Effect of solvents on conversion of 4-nitrobenzaldehyde to Benzaldehyde Benzamide 76
4-nitrobenzamide using catalyst 1. Tolualdehyde Toluamide 74
9 4-Nitrobenzaldehyde 4-Nitrobenzamide 84
Benzaldehyde Benzamide 74
Table 2. Effect of base in the conversion of 4-nitrobenzaldehyde to Tolualdehyde Toluamide 77
4-nitrobenzamide using complex 1 a
Isolated yield after column chromatography (average of two runs).
Entry Solvent Base Temp. Time Yield
(°C) (h) (%)a

1 Xylene NaHCO3 140 48 36 transformation proceeded via the formation of a RuIV(OH)(imine)

2 Acetonitrile NaHCO3 78 48 76 intermediate, as proposed by Crabtree and co-workers.[66] When
3 Benzene NaHCO3 80 48 33 compared to other ruthenium complexes,[12a] the percent yields
4 Dichloromethane NaHCO3 40 48 29 were higher for the new ruthenium complexes.
5 Chloroform NaHCO3 64 48 26
6 Toluene NaHCO3 115 24 86
7 Toluene KHCO3 115 24 85 Alkane Oxidation
8 Toluene CH3COONa 115 24 <20 The catalytic ability of the ruthenium(II) complexes towards the
9 Toluene Et3N 115 24 <20 oxidation of alkanes such as cyclohexane and ethylbenzene was
10 Toluene — 115 48 — explored using m-CPBA as oxidant in a dichloromethane–
11 Toluene NaHCO3 115 48b — acetonitrile solvent mixture (3:1, v/v) at room temperature for
a
Isolated yield after column chromatography (average of two runs). 48 h under nitrogen atmosphere (Table 4). In order to optimize
b
Reaction carried out in the absence of catalyst. the reaction conditions, the effects of time (Fig. 3) and different
catalyst/substrate ratio (Fig. 4) were tested[75] using catalyst 1
as a model. Using the optimized conditions, the oxidation of al-
kanes using all the synthesized ruthenium(II) complexes were
substituent (nitro) on benzaldehyde gave slightly higher yields carried out. It was observed that the oxidation of cyclohexane
when compared to that of benzaldehyde. Electron-donating proceeded to give cyclohexanol as the major product, along with
substituent (methyl) on benzaldehyde gave slightly lower yields cyclohexanone and ɛ-caprolactone as minor products, where
23

compared with benzaldehyde. We believe that the catalytic ɛ-caprolactone is the over-oxidized product of the oxidation of

Appl. Organometal. Chem. 2014, 28, 18–26 Copyright © 2013 John Wiley & Sons, Ltd. wileyonlinelibrary.com/journal/aoc
 M. Nirmala et al.

Table 4. Catalytic oxidation of alkanes using ruthenium(II)

hydroxyquinoline–thiosemicarbazone complexes 80

Ru(II) complex / R.T OH O

m- CPBA/
60

Conversion (%)
CHCl3/CH3CN +
CyOH
CyO
Caprolactone
40
Complex Substrate Product Yield (%)

1 Cyclohexane Cyclohexanol 78
Cyclohexanone <11 20
ε-Caprolactone <10
Ethylbenzene 1-Phenylethanol 76
Acetophenone 17 0
2 Cyclohexane Cyclohexanol 75 0 10 20 30 40 50 60 70 80
Cyclohexanone 10 Time (hrs)
ε-Caprolactone <10
Figure 3. Effect of time on oxidation of cyclohexane catalyzed by com-
Ethylbenzene 1-Phenylethanol 73 plex 1 in the presence of m-CPBA.
Acetophenone 16
3 Cyclohexane Cyclohexanol 78
Cyclohexanone 10
ε-Caprolactone <10
80
Ethylbenzene 1-Phenylethanol 69
Acetophenone 13 70
4 Cyclohexane Cyclohexanol 77 CyOH
CyO
Cyclohexanone 11 60
Products yield (%)

Caprolactone
ε-Caprolactone <10
Ethylbenzene 1-Phenylethanol 74 50

Acetophenone 14
40
5 Cyclohexane Cyclohexanol 74
Cyclohexanone 12 30
ε-Caprolactone 11
Ethylbenzene 1-Phenylethanol 68 20
Acetophenone 12
10
6 Cyclohexane Cyclohexanol 76
Cyclohexanone 12 0
ε-Caprolactone 10 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8
Ethylbenzene 1-Phenylethanol 71 cyclohexane
Acetophenone 16
7 Cyclohexane Cyclohexanol 74 Figure 4. Effect of substrate concentration on oxidation of cyclohexane
catalyzed by complex 1.
Cyclohexanone 10
ε-Caprolactone <10
Ethylbenzene 1-Phenylethanol 72
cyclohexanone by excess or unreacted m-CPBA. It is well known
Acetophenone 21
that m-CPBA is a quantitative reagent for the conversion of cyclic
8 Cyclohexane Cyclohexanol 78
ketones to the corresponding lactones (Bayer–Villiger oxidation)
Cyclohexanone 10
in the absence of any metal catalyst and so the ɛ-caprolactone
ε-Caprolactone <10
is not the metal-catalyzed product. Interestingly, only 50%
Ethylbenzene 1-Phenylethanol 75
of the oxidized products were formed under air. Also, when
Acetophenone 18
H2O2–t-BuOOH was used as the oxidant only trace amounts of
9 Cyclohexane Cyclohexanol 75
the oxidized products are formed, demonstrating that the ruthe-
Cyclohexanone <10
nium(II) complexes are not effective as catalysts for these
ε-Caprolactone <10
oxidants. The most efficient conversions were found in the case
Ethylbenzene 1-Phenylethanol 69
of cyclohexane with all catalysts (up to 78%), as can be seen in
Acetophenone 17
Table 4. Similarly, ruthenium(II)-catalyzed oxidation of ethylben-
Blanka Cyclohexane Cyclohexanol 35
zene led to the formation of the corresponding alcohol and
Cyclohexanone —
ketone in yields of 76–68 % and 21–12 % respectively. On com-
ε-Caprolactone —
paring the present catalytic system with that of other ruthe-
Ethylbenzene 1-Phenylethanol 27
nium(II) complexes previously reported[76,77] for this conversion,
Acetophenone —
our new complexes showed better catalytic efficiency. The per-
a
Reaction carried out in the absence of catalyst. cent yields were comparatively higher under the same reaction
24

conditions and media.

wileyonlinelibrary.com/journal/aoc Copyright © 2013 John Wiley & Sons, Ltd. Appl. Organometal. Chem. 2014, 28, 18–26
Ru(II) complexes of hybrid 8-hydroxyquinoline–thiosemicarbazone ligands

Catalytic N-Alkylation of Amine Conclusions

The ruthenium(II) hydroxyquinoline–thiosemicarbazone com- A series of new hexa-coordinated ruthenium(II) Schiff base
plexes catalyzed the N-alkylation of amine with alcohols in the complexes were synthesized from hydroxyquinoline–
presence of KOtBu. The yields were obtained by 1H NMR integra- thiosemicarbazone-based ligands and ruthenium(II) precursor
tion compared to the internal standard. As shown in the Table 5, complexes. An octahedral structure was tentatively proposed
benzyl alcohols reacted smoothly to give the corresponding for all the complexes based on the analytical and spectral results.
products in good yields (71–86%) whereas, p-methoxybenzyl al- The complexes were employed as catalyst for organic reactions
cohol gave the corresponding product in moderate yield (up to such as aldehyde-to-amide conversion, alkane oxidation and
71%). Complexes containing L1 ligand is a significantly efficient N-alkylation. The aldehyde-to-amide conversion reaction was car-
catalyst compared to the other complexes. When compared to ried out in the presence of NH2OH.HCl and base. time and C:S ra-
earlier reported systems, the catalyst loadings were very low tios were optimized for the above conversion and the effects of
and the reaction conditions were very mild in the present cata- different solvents and bases were also investigated. The maxi-
lytic system.[78,79] mum yield of amides was observed up to 86% for the substrate
4-nitrobenzaldehyde under optimized conditions. Alkane oxida-
tion was performed at room temperature in the presence
m-CPBA as oxidant and dichloromethane/acetonitrile solvent
Table 5. N-Alkylation of benzylamine catalyzed by ruthenium(II) mixture as reaction medium. The maximum yield of 78%
hydroxyquinoline–thiosemicarbazone complexes
obtained for the oxidation of cyclohexane. N-Alkylation was car-
ried out at 110–150°C in the presence of KOtBu under nitrogen
atmosphere. N-Alkylation of benzylamine showed a maximum
OH yield of 86%. Overall, the new ruthenium complexes possess effi-
NH2 NH cient catalytic activities for the above three organic conversions.
Ru(II) complex
KOtBu, 100 °C, 6 h
+
Supporting information
R
Supporting information may be found in the online version of
R
this article.
(R = H or OCH3)
Acknowledgments
We are thankful to IISC, Bangalore, Department of Chemistry, MKU,
Complex Medium Product Yield
(%)a Madurai and SAIF, Cochin, for providing instrumental facilities.

1 Benzyl alcohol N-Phenylbenzylamine 86

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