Synthesis and characterization of ruthenium complexes with 1-aryl-2-mercaptoimidazole ligands

Article abstract of DOI:10.1016/j.jorganchem.2012.01.010

Reactions of the vinyl ruthenium starting material Ru(CHCHPh)Cl(CO) (PPh₃)₂ (1) with 1-aryl-2-mercaptoimidazole (HLa, aryl = 4-chloro-phenyl; HLb, aryl = 4-methyl-phenyl; HLc, aryl = 4-nitro-phenyl) in the presence of sodium methoxid

Full text of DOI:10.1016/j.jorganchem.2012.01.010

Journal of Organometallic Chemistry 705 (2012) 34e38
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Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Synthesis and characterization of ruthenium complexes
with 1-aryl-2-mercaptoimidazole ligands
,
a
,
,b,
**
Ai-Quan Jia a , Qing Ma b, Qun Chen b, Hua-Tian Shi a, Wa-Hung Leung c, Qian-Feng Zhang a
*
a Institute of Molecular Engineering and Applied Chemistry, Anhui University of Technology, Ma’anshan, Anhui 243002, PR China
b Department of Applied Chemistry, School of Petrochemical Engineering, Changzhou University, Jiangsu 213164, PR China
c Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
Reactions of the vinyl ruthenium starting material Ru(CH]CHPh)Cl(CO)(PPh3)2 (1) with 1-aryl-2-
mercaptoimidazole (HLa, aryl ¼ 4-chloro-phenyl; HLb, aryl ¼ 4-methyl-phenyl; HLc, aryl ¼ 4-nitro-
phenyl) in the presence of sodium methoxide in dichloromethane and methanol afforded [Ru(CH]
Received 26 November 2011
Received in revised form
9 January 2012
CHPh)(
contaminant with formation of styrene as byproduct. Interactions of 1 with HLa in dichloromethane
led to isolation of a novel dinuclear ruthenium complex [(CO)(PPh3)(CHNCH2Ph)Ru( -Cl)2( -S)RuCl(-
k k
2-L)(CO)(PPh3)2] (2ae2c). Treatment of 1 with HL in THF gave [RuCl( 2-L)(CO)(PPh3)2] (3ae3c)
Accepted 16 January 2012
m
m
Keywords:
Ruthenium
Vinyl
1-Aryl-2-mercaptoimidazole
NeH bond addition
X-ray structure
CO)(PPh3)] (4a) via NeH bond addition to styryl ligand. Complexes 2ae2c, 3ae3c, and 4a were char-
acterized by microanalyses, IR, and (1H, 13C, 31P) NMR spectroscopies. The molecular structures of 3ae3c
and 4a have been determined by single-crystal X-ray diffraction.
Ó 2012 Elsevier B.V. All rights reserved.
1. Introduction
extensive interest on the coordination chemistry of such mercap-
toimidazoles as ligands for metal complexes, there has been little
Since the vinyl ruthenium complexes [Ru(CR1]CHR2)
Cl(CO)(PPh3)2] were firstly prepared by insertion of the alkyne into
the RueH bond of RuHCl(CO)(PPh3)3 [1], considerable effort has
been focused on the preparation, reactivity and mechanism study
of such complexes [2e15]. Reactions related to vinyl ruthenium
complexes mainly include (i) insertion of small molecules, such as
exploration of 1-aryl-2-mercaptoimidazole. Apart from one study
[25] in which MimPh (MimPh ¼ 2-mercapto-1-phenylimidazole)
was used to construct a polymetric compound [Ag5I5(MimPh)4]n.
Herein, we report the reactions of vinyl ruthenium complexes with
1-aryl-2-mercaptoimidazole ligands (Scheme 1).
CS2 and CO2, into rutheniumealkenyl bond [2], (ii) addition of
p-
2. Results and discussion
acid ligands such as carbon monoxide and isocyanide to yield
coordinatively saturated compounds and subsequent migration of
the vinyl group to form acyl complexes [3], (iii) substitution of
chloride by bi- or polydentate ligand [12e18].
2.1. Synthesis of ruthenium complexes (2ae2c), (3ae3c), and (4a)
from vinyl ruthenium complex
1-Methyl-2-mercaptoimidazole (also referred to as 1-
methylimidazole-2-thiol, methimazole) [19e23], as well as 1-
tertbutyl-2-mercaptoimidazole [24], can form stable complexes
with a wide range of main group and transition metal ions. It could
act as monodentate ligand in the neutral form and bidentate, three-
electron S,N-donor ligand after deprotonation. Despite the
It is well known that Wilton-Ely and coworkers have concen-
trated on the reactivity of alkenyl complexes Ru(CH]CHPh)
Cl(CO)(PPh3)2 and Ru(CH]CHC6H4Me-4)Cl(CO)(BTD)(PPh3)2]
(BTD ¼ 2,1,3-benzothiadiazole, a labile ligand), toward a series of
bi- and tridentate ligands involving carboxylates, dithiocarba-
mates, dithiophosphinates, nitrogenesulfur and nitrogeneoxygen
mixed donors, polypyrazolylborate, and sulfur macrocycle ([9]
aneS3) [12e18]. A remarkable rearrangement of vinyl to sulfur
atom was observed based on bulky N-heterocyclic carbenes
dithiocarboxylate ligands [14]. In the initial experiments we
investigated the reactions of 1-aryl-2-mercaptoimidazole
* Corresponding author. Tel./fax: þ86 555 2312041.
** Corresponding author. Institute of Molecular Engineering and Applied
Chemistry, Anhui University of Technology, Ma’anshan, Anhui 243002, PR China.
Tel./fax: þ86 555 2312041.
E-mail address: jaiquan@ahut.edu.cn (A.-Q. Jia).
(HL) with Ru(CH]CHPh)Cl(CO)(PPh3)2 (1) using a slightly
0022-328X/$ e see front matter Ó 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2012.01.010

A.-Q. Jia et al. / Journal of Organometallic Chemistry 705 (2012) 34e38
35
Scheme 1. Synthesis of Complexes 2ae2c, 3ae3c and 4a.
modified procedure reported by Wilton-Ely and coworkers [15].
The expected vinyl ruthenium complexes [Ru(CH]CHPh)(k2
metallacycle. And it is obvious that the original C]C double bond of
vinyl turns to be a typical CeC single bond (C(1)eC(2) 1.546(7) Å),
inducting of chirality at C1. The terminal Ru(1)eCl(2) bond length is
2.413(2) Å, shorter than those of bridged RueCl bond distance
(2.46e2.53 Å) in 4a.
-
L)(CO)(PPh3)2] (2ae2c) were obtained easily. However, treatment
of 1 with HL without base in THF at room temperature gave
[RuCl(k
2-L)(CO)(PPh3)2] (3ae3c) in high yields, the styryl ligand in
the starting ruthenium compound was substituted by Lꢀ as
a bidentate ligand, releasing styrene. The PhCH]CH2 proton
signals (5.74 (dd, J ¼ 17.6 Hz, 1H), 5.23 (d, J ¼ 10.8 Hz, 1H)) [26]
could be clearly observed in the 1H NMR spectra of the crude
products of 3ae3c. The recrystallization of 3ae3c from a THF/
cyclohexane mixture (1:3) afforded analytically pure crystals
suitable for an X-ray diffraction (vide infra), which clearly iden-
tified the solid-state structure of this species. In fact, displacement
of styryl ligand by benzophenone imine and 2-vinylpyridine on
Ru(CH]CHPh)Cl(CO)(PiPr3)2 in refluxing toluene has already
been reported [27]. A pure sample of [(CO)(PPh3)(CHNCH2Ph)
2.3. NMR characterization of complexes (2ae2c), (3ae3c), and
(4a)
Complexes 2ae2c were examined by multinuclear NMR spec-
troscopy and readily identified as vinyl complexes having PhCH]
CH moiety compared to related compounds [15]. The 1H NMR
spectrum of 2a showed both vinylic protons and imidazole ring
protons (H4, H5, Chart 1), appearing at 7.92 (H
a
, d, 3JHH ¼ 16.4 Hz),
3
5.94 (H
b
, d, JHH ¼ 16.4 Hz), 6.00 (s, im-H), 6.39 (s, im-H) ppm,
respectively. Three low field triplets at 135.0 (t, JCP ¼ 3.6 Hz), 156.3
(t, JCP ¼ 11.0 Hz) and 206.3 ppm (t, JCP ¼ 16.2 Hz) were assigned to
Ru(m-Cl)2(m-S)RuCl(CO)(PPh3)] (4a) was obtained only in small
quantity from interactions of 1 with HLa in dichloromethane
followed by recrystallization of the crude product in CH2Cl2/
cyclohexane mixture (1:2). Possibly, substitution of PPh3 by LHa
via sulfur atom, followed by addition of NeH bond in HLa to
phenylethenyl ligand, and trapping of chloride from dichloro-
methane solvent took place during the formation of 4a according
to its molecular structure. However, reactions of 1 with HLb and
HLc in chloromethane or chloroform led to isolation of 3b and 3c,
respectively (Scheme 1).
the b-carbon of the vinyl, a-carbon of the vinyl and the carbonyl
ligand, respectively. The resonances of C5 (114.7 ppm), C4
2.2. Single-crystal X-ray diffraction study of complexes (3ae3c)
and (4a)
The structures of complexes 3ae3c and 4a were established by
an X-ray diffraction study. The ORTEP representation of the
molecular structures of them with selected interatomic distances
and angles are shown in Figs. 1e4. Based on the crystallographic
data, complexes 3ae3c can be formulated as an 18-electron species
with the formally six-coordinate Ru(II) atom. The ruthenium atoms
in 3ae3c are coordinated by 1-arylimidazole-2-thiolate, acting as
a bidentate N,S-donor. The PeRueP angles for complexes 3ae3c
with mutually trans PPh3 ligands are in the range of 175.21(3)e
177.02(34)ꢁ. The bond distances of RueS in 3ae3c lie in the range
of 2.4383(9)e2.4948(8) Å, shorter than that in complex Ru(CH]
2-MI)(CO)(PPh3)2] (MI
¼
1-methylimidazole-2-
Fig. 1. Molecular structure of 3a. Hydrogen atoms are omitted for clarity. Selected
bonds (Å) and angles (ꢁ): Ru(1)eC(1) 1.861(3), Ru(1)eS(1) 2.4948(8), Ru(1)eN(1)
2.164(2), Ru(1)eP(1) 2.3952(8), Ru(1)eP(2) 2.3843(7), Ru(1)eCl(1) 2.3992(8), S(1)e
C(2) 1.714(3), N(1)eC(2) 1.316(3), N(1)eC(3) 1.370(3), N(1)eRu(1)eS(1) 67.33(6), P(1)e
Ru(1)eP(2) 175.43(2), Cl(1)eRu(1)eS(1) 160.93 (3), C(1)eRu(1)eN(1) 167.40(10).
CHC6H4Me-4)(
k
thiolate, 2.5907(16) Å) [15]. The structure of 4a clearly shows
addition of NeH bond of HLa to the styryl ligand to give a new
N(2)eC(1) bond (1.507(6) Å) as an integral part of a five-membered

36
A.-Q. Jia et al. / Journal of Organometallic Chemistry 705 (2012) 34e38
Fig. 4. Molecular structure of 4a. Hydrogen atoms are omitted for clarity. Selected
bonds (Å) and angles (ꢁ): Ru(1)eC(6) 1.821(5), Ru(1)eS(1) 2.417(1), Ru(1)eCl(2)
2.413(2), Ru(1)eCl(3) 2.506(2), Ru(1)eCl(4) 2.490(2), Ru(1)eP(2) 2.295(2), Ru(2)eC(7)
1.811(6), Ru(2)eC(1) 2.097(5), Ru(2)eP(1) 2.334(2), Ru(2)eS(1) 2.430(1), Ru(2)eCl(3)
2.535(2), Ru(2)eCl(4) 2.465(1), C(1)eC(2) 1.546(7), C(2)eC(11) 1.492(9), C(1)eN(2)
1.507(6), C(3)eN(2) 1.328(6), C(3)eS(1) 1.748(5), Cl(3)eRu(1)eC(6) 174.4(2), Cl(4)e
Ru(1)eP(2) 177.7(5), Cl(2)eRu(1)eS(1) 167.0(5), S(1)eRu(2)eP(1) 175.3(5), C(7)e
Ru(2)eCl(4) 174.5(2), Cl(3)eRu(2)eC(1) 163.3(1), S(1)eRu(1)eP(2) 96.9(5).
Fig. 2. Molecular structure of 3b. Hydrogen atoms are omitted for clarity. Selected
bonds (Å) and angles (ꢁ): Ru(1)eC(1) 1.850(3), Ru(1)eS(1) 2.4545(9), Ru(1)eN(1)
2.165(2), Ru(1)eP(1) 2.3836(8), Ru(1)eP(2) 2.3979(9), Ru(1)eCl(1) 2.4056(8), S(1)e
C(2) 1.723(3), N(1)eC(2) 1.320(4), N(1)eC(3) 1.363(4), N(1)eRu(1)eS(1) 67.54(7),
P(1)eRu(1)eP(2) 175.21(3), Cl(1)eRu(1)eS(1) 160.99 (3), C(1)eRu(1)eN(1) 167.55(12).
(123.6 ppm) and NCN (153.5 ppm) in the imidazole ring were
shown as three singlets. There was one 31P signal at 42.0 ppm in the
31P NMR, indicating trans-position of the two phosphine ligands.
Similar spectroscopic data were observed for complexes 2b and 2c.
The NMR data for 3ae3c are in agreement with their crystal
structures. One 31P signal, around 38.3 ppm, was observed in their
31P NMR spectra. Three singlets at 114.5, 123.0, and 152.3 ppm were
identified as C5, C4 and NCN of the imidazole ring, respectively, shift
upfield a little compared to those in 2a. Although complex 4a could
not be obtained in sufficient quantities to allow the complete
analytical and spectroscopic characterization, its 1H NMR spectrum
was readily assigned based on the comparison with that of 2a. No
resonances due to vinylic
a and b-protons were observed. Instead,
new resonances at 2.77 and 4.27 ppm were noted, which could be
assigned to RuCHCH2Ph protons. The imidazole protons, appearing
at 6.76 and 5.52 ppm, shift upfield compared to free ligand
(6.84 ppm). There were two 31P signals, appeared at 45.5 (PPh3) and
42.8 (PPh3) ppm, in 31P NMR spectrum of 4a.
3. Experimental
3.1. General comments
All the operations were carried out under pure nitrogen atmo-
sphere using standard Schlenk techniques. Solvents were distilled
prior to use, [Ru(CH]CHPh)Cl(CO)(PPh3)2] [1], and 1-aryl-2-
mercaptoimidazole [28] were prepared according to modified
literature methods. NMR spectra were recorded on a BrukerALX400
spectrometer operating at 400, 100, and 162 MHz for 1H, 13C and
31P, respectively. Chemical shifts (
reference to SiMe4 (1H), the residual solvent peak (13C) and H3PO4
31P). Infrared spectra (KBr) were recorded on a PerkineElmer 16 PC
d, ppm) were reported with
(
FT-IR spectrophotometer with the use of pressed KBr pellets, and
elemental analyses for C and H were carried out on an Elementar III
Vario EI analyzer.
Fig. 3. Molecular structure of 3c. Hydrogen atoms are omitted for clarity. Selected
bonds (Å) and angles (ꢁ): Ru(1)eC(1) 1.839(4), Ru(1)eS(1) 2.4383(9), Ru(1)eN(1)
2.158(3), Ru(1)eP(1) 2.3899(9), Ru(1)eP(2) 2.3892(9), Ru(1)eCl(1) 2.4141(10), S(1)e
C(4) 1.720(3), N(1)eC(4) 1.312(4), N(2)eC(4) 1.383(4), N(1)eRu(1)eS(1) 67.87(7), P(1)e
Ru(1)eP(2) 177.02(3), Cl(1)eRu(1)eS(1) 157.71 (4), C(1)eRu(1)eN(1) 170.55(13).
Chart 1. Numbering scheme for the 1-arylimidazole-2-thiolate (L) and styryl ligand.

A.-Q. Jia et al. / Journal of Organometallic Chemistry 705 (2012) 34e38
37
3.2. Preparation of [Ru(CH]CHPh)(CO)(PPh3)2(
k
2-L)] (2ae2c)
Me] ppm. Anal. Calc. for C55H46N2OP2RuS: C 69.75; H 4.90; N
2.96; Found: C, 69.80; H, 4.88; N 2.99. For 2c, yield 90.0 mg (92%).
To a suspension of [Ru(CH]CHPh)Cl(CO)(PPh3)2] (80.0 mg,
0.10 mmol) and 1-aryl-2-mercaptoimidazole (0.10 mmol) in
dichloromethane (5 mL) and methanol (2 mL) was added MeONa
(6.0 mg, 0.12 mmol) in methanol (3 mL), the mixture was stirred
for 1 h at room temperature, the solvent volume was concen-
trated under reduced pressure until pale yellow-green crystals
precipitated. The product was filtered, washed with methanol
(5 mL) and hexane (10 mL) and dried. For 2a, yield: 83.0 mg
IR (KBr): 1918
n .
(CO) cmꢀ1 31P NMR (CDCl3): 42.0 [s, PPh3] ppm.
1H NMR (CDCl3): 5.95 [d, H
b
, 1H, J ¼ 16.4 Hz], 6.10 [br, im-CH, 1H],
6.41 [br, im-CH, 1H], 6.48 [d, o-C6H5, 2H, J ¼ 7.6 Hz], 6.90 [t, p-
C6H5, 1H, JHH ¼ 7.2 Hz], 7.02 [t, m-C6H5, 2H, JHH ¼ 7.2 Hz], 7.16 [d,
C6H4, 2H, J ¼ 8.8 Hz], 7.20e7.30, 7.48e7.52 [m ꢂ 2, PC6H5, 30H],
7.91 [dt, H
13C NMR (CDCl3):
J ¼ 9.9 Hz], 154.4 [s, NCN], 145.0 [s, ipso-Ph], 142.0 [s, ipso-C6H4],
141.5 [s, p-C6H4], 135.1 [t, C
a
, 1H, JHH ¼ 16.4 Hz], 8.08 [d, C6H4, 2H, J ¼ 9.2 Hz] ppm.
d
206.2 [t, CO, JCP ¼ 16.2 Hz], 155.6 [t, C
a,
(86%). IR (KBr): 1924
n
(CO) cmꢀ1
.
31P NMR (CDCl3): 42.0 [s,
, 1H, J ¼ 16.4 Hz], 6.00 [br,
b
, J ¼ 3.6 Hz], 134.3 [t, o/m-PC6H5,
PPh3] ppm. 1H NMR (CDCl3): 5.94 [d, H
b
JCP ¼ 5.4 Hz], 132.8 [t, ipso-PC6H5, JCP ¼ 21.3 Hz], 129.2 [s, p-
PC6H5)], 127.6 [s, o/m-Ph], 127.5 [t, o/m-PC6H5, JCP ¼ 4.6 Hz], 124.5
[s, o/m-C6H4], 124.3 [s, o/m-C6H4], 124.2 [s, o/m-Ph], 123.5 [s, o/m-
Ph], 121.7 [s, NC4H], 114.1 [s, NC5H] ppm. Anal. Calc. for
C54H43N3O3P2RuS: C 66.32; H 4.43; N 4.30; Found: C, 66.38; H,
4.44; N 4.34.
im-CH, 1H], 6.39 [br, im-CH, 1H], 6.47 [d, C6H4, 2H, J ¼ 7.6 Hz], 6.78
[d, o-C6H5, 2H, J ¼ 8.4 Hz], 6.88 [t, p-C6H5, 1H, JHH ¼ 7.2 Hz], 7.16
[t, m-C6H5, 2H, JHH ¼ 7.2 Hz], 7.20e7.32, 7.46e7.56 [m ꢂ 2, PC6H5,
30H], 7.92 [d, H
a
, 1H, JHH ¼ 16.4 Hz] ppm. 13C NMR (CDCl3):
d
206.3 [t, CO, JCP ¼ 16.2 Hz], 156.3 [t, C , J ¼ 11.0 Hz], 153.5 [s,
a
NCN], 141.7 [s, ipso-Ph], 135.3 [s, ipso-C6H4], 135.0 [t,
Cb,
3.3. Preparation of [RuCl(CO)(PPh3)2(
k
2-L)] (3ae3c)
J ¼ 3.6 Hz], 134.3 [t, o/m-PC6H5, JCP ¼ 5.4 Hz], 132.9 [t, ipso-PC6H5,
JCP ¼ 21.2 Hz], 131.7 [s, o/m-C6H4], 129.1 [s, p-PC6H5], 128.8 [s, o/m-
C6H4], 127.5 [s, o/m-Ph], 127.5 [t, o/m-PC6H5, JCP ¼ 4.6 Hz], 124.3 [s,
p-C6H4], 123.6 [s, NC4H], 123.3 [s, o/m-Ph], 123.3 [s, p-Ph], 114.7 [s,
NC5H] ppm. Anal. Calc. for C54H43ClN2OP2RuS: C 67.07; H 4.49; N
2.90; Found: C, 66.99; H, 4.47; N, 2.94. For 2b, Yield: 80.4 mg
To solution of [Ru(CH]CHPh)Cl(CO)(PPh3)2] (40.0 mg,
a
0.05 mmol) in THF (10 mL) was added 1-aryl-2-mercaptoimidazole
(0.05 mmol), the mixture was stirred overnight to yield a yellow or
red solution. The solvent was evaporated in vacuum and washed
with n-hexane. Slow diffusion of cyclohexane to THF solution
afforded yellow or red crystals of 3ae3c. For 3a, yield: 40.5 mg
(85%). IR (KBr): 1916
n
(CO) cmꢀ1
.
31P NMR (CDCl3): 42.0 [s,
, 1H,
PPh3] ppm. 1H NMR (CDCl3): 2.25 [s, Me, 3H], 5.97 [d, H
b
(90%). IR (KBr): 1921
n .
(CO) cmꢀ1 31P NMR (CDCl3): 38.3 [s,
J ¼ 14.4 Hz], 6.00 [br, im-CH, 1H], 6.37 [br, im-CH, 1H], 6.48 [d,
C6H4, 2H, J ¼ 6.8 Hz], 6.69 [d, o-C6H5, 2H, J ¼ 6.4 Hz], 6.89 [t, p-
C6H5, 1H, JHH ¼ 7.2 Hz], 6.96e7.06 [m, m-C6H5 þ C6H4, 4H],
PPh3] ppm. 1H NMR (CDCl3): 5.91 [d, im-CH, 1H, J ¼ 1.6 Hz], 6.30 [d,
im-CH, 1H, J ¼ 2.0 Hz], 6.78 [d, C6H4, 2H, J ¼ 8.8 Hz], 7.20 [d, C6H4,
2H, J ¼ 8.8 Hz], 7.27e7.32, 7.57e7.62 [m ꢂ 2, PC6H5, 30H] ppm. 13
C
7.01e7.22, 7.45e7.55 [m ꢂ 2, PC6H5, 30H], 7.94 [d, H
a
, 1H,
206.4 [t, CO,
, J ¼ 10.8 Hz], 153.3 [s, NCN], 141.8[s,
ipso-Ph], 136.0 [s, ipso-C6H4], 134.9 [t, C
, J ¼ 3.6 Hz], 134.3 [t, o/m-
JHH
¼
14.4 Hz] ppm. 13C NMR (CDCl3):
d
NMR (CDCl3):
d
206.2 [t, CO, JCP ¼ 16.0 Hz], 152.3 [s, NCN], 135.1 [s,
JCP ¼ 16.0 Hz], 156.7 [t, C
a
ipso-C6H4], 134.9 [t, o/m-PC6H5, JCP ¼ 5.5 Hz], 133.0 [t, ipso-PC6H5,
JCP ¼ 21.8 Hz], 132.4 [s, o/m-C6H4], 130.0 [s, p-PC6H5], 129.7 [s, o/m-
C6H4], 128.1 [t, o/m-PC6H5, JCP ¼ 4.6 Hz], 126.1 [s, p-C6H4], 123.0 [s,
NC4H], 114.5 [s, NC5H] ppm. Anal. Calc. for C46H36Cl2N2OP2RuS: C
61.47; H 4.04; N 3.12; Found: C, 61.45; H, 4.09; N 3.13. For 3b,
b
PC6H5, JCP ¼ 4.4 Hz], 134.3 [s, o/m-C6H4], 133.0 [t, ipso-PC6H5,
JCP ¼ 21.1 Hz], 129.2 [s, o/m-C6H4], 129.1 [s, p-PC6H5], 127.5 [s, o/m-
Ph], 127.4 [t, o/m-PC6H5, JCP ¼ 4.6 Hz], 124.3 [s, p-C6H4], 123.2 [s, o/
m-Ph], 122.8 [s, p-Ph], 122.4 [s, NC4H], 115.1 [s, NC5H], 20.9 [s,
38.6 mg, yield (88%). IR (KBr): 1919
n .
(CO) cmꢀ1 31P NMR (CDCl3):
Table 1
Crystallographic data and experimental details for complexes (3a$0.5C6H12, 3b$0.5C6H12, 3c$CH2Cl2) and (4a$CH2Cl2).
Complex
3a$0.5C6H12
3b$0.5C6H12
3c$CH2Cl2
4a$CH2Cl2
Empirical formula
Formula weight
Crystal system
a (Å)
b (Å)
c (Å)
C49H42Cl2N2OP2RuS
940.82
C50H45ClN2OP2RuS
920.40
C47H38Cl3N3O3P2RuS
994.22
C56H46N2O2Cl6P2SRu2
1290.31
Monoclinic
19.696(2)
11.0868(12)
26.305(3)
90
102.4210(10)
90
5609.8(10)
P21/n
Monoclinic
10.885(2)
14.678(3)
27.451(5)
90
90.887(2)
90
4385.4(14)
P21/c
Monoclinic
10.8794(10)
14.6864(13)
27.565(2)
90
91.0950
90
4403.4(7)
P21/c
Monoclinic
18.862(3)
14.552(2)
17.857(3)
90
110.342(2)
90
4595.6(11)
P21/c
a
b
g
(ꢁ)
(ꢁ)
(ꢁ)
V (Å3)
Space group
Z
4
4
4
4
Dcalc (g cmꢀ3
)
1.425
1.388
1.437
1.528
Temperature (K)
296(2)
296(2)
296(2)
296(2)
F(000)
1928
0.639
1896
0.576
2024
0.674
2602
0.961
m
(Mo-K
a
) (mmꢀ1
)
Total refln
26826
27139
28337
34422
Independent refln
9941
10089
10495
12795
Rint
0.0288
0.0502
0.0450
0.0525
R1a, wR2b (I > 2
s(I))
0.0391, 0.1013
0.0548, 0.1110
508
0.0423, 0.0919
0.0770, 0.1058
509
0.0505, 0.1241
0.0791, 0.1367
596
0.0570, 0.1604
0.1054, 0.1905
680
R1, wR2 (all data)
Parameter
GoFc
1.023
0.987
0.981
1.008
P
P
a
R1 ¼ jjFoj ꢀ jFcjj= jFoj.
P
P
wR2 ¼ ½ wðjFo2j ꢀ jFc2jÞ2= wjFo2j2ꢃ1=2
.
b
c
P
GoF ¼ ½ wðjFoj ꢀ jFcjÞ2=ðNobs ꢀ NparamÞꢃ1=2
.

38
A.-Q. Jia et al. / Journal of Organometallic Chemistry 705 (2012) 34e38
38.4 [s, PPh3] ppm. 1H NMR (CDCl3): 2.28 [s, Me, 3H], 5.90 [d, im-
CH, 1H, J ¼ 2.0 Hz], 6.26 [d, im-CH, 1H, J ¼ 1.6 Hz], 6.69 [d, C6H4, 2H,
J ¼ 8.8 Hz], 7.03 [d, C6H4, 2H, J ¼ 8.0 Hz], 7.22e7.28, 7.58e7.63
Acknowledgments
This project was supported by the Natural Science Foundation of
China (20771003) and the Hong Kong Research Grants Council
(project no. 601708).
[m ꢂ 2, PC6H5, 30H] ppm. 13C NMR (CDCl3):
d 206.2 [t, CO,
JCP ¼ 15.8 Hz], 152.0 [s, NCN], 136.8 [s, ipso-C6H4], 134.9 [t, o/m-
PC6H5, JCP ¼ 5.5 Hz], 134.1 [s, o/m-C6H4], 133.1 [t, ipso-PC6H5,
JCP ¼ 21.7 Hz], 130.1 [s, o/m-C6H4], 129.9 [s, p-PC6H5], 128.1 [t, o/m-
PC6H5, JCP ¼ 4.8 Hz], 125.6 [s, p-C6H4], 121.8 [s, NC4H], 114.9 [s,
NC5H], 21.4 [s, Me] ppm. Anal. Calc. for C47H39ClN2OP2RuS: C 64.27;
H 4.48; N 3.19; Found: C, 64.19; H, 4.44; N, 3.23. For 3c, 38.6 mg,
Appendix A. Supplementary material
CCDC 854737e854740 contain the supplementary crystallo-
graphic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via www.
ccdc.cam.ac.uk/data_request/cif.
yield (85%). IR (KBr): 1940
n .
(CO) cmꢀ1 31P NMR (CDCl3): 38.2 [s,
PPh3] ppm. 1H NMR (CDCl3): 6.03 [d, im-CH, 1H, J ¼ 1.6 Hz], 6.32 [d,
im-CH, 1H, J ¼ 1.6 Hz], 6.71 [d, C6H4, 2H, J ¼ 3.7 Hz], 7.24e7.29,
7.57e7.62 [m
ꢂ
2, PC6H5, 30H], 8.12 [d, C6H4, 2H,
J ¼ 3.6 Hz] ppm. 13C NMR (CDCl3):
d
205.3 [t, CO, JCP ¼ 15.3 Hz],
References
152.9 [s, NCN], 145.1 [s, ipso-C6H4], 141.2 [s, p-C6H4], 134.4 [t, o/m-
PC6H5, JCP ¼ 5.4 Hz], 132.4 [t, ipso-PC6H5, JCP ¼ 21.9 Hz], 129.6 [s, p-
PC6H5], 127.6 [t, o/m-PC6H5, JCP ¼ 4.8 Hz], 126.3 [s, o/m-C6H4], 124.9
[s, o/m-C6H4], 120.6 [s, NC4H], 113.4 [s, NC5H] ppm. Anal. Calc. for
C46H36ClN3O3P2RuS: C 60.72; H 3.99; N 4.62; Found: C, 60.45; H,
4.03; N, 4.67.
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methane/n-hexane. Yield: 18.0 mg (30%). IR (KBr): 1918, 1921
n
(CO) cmꢀ1
.
31P NMR (CDCl3): 45.5, 42.1 [s ꢂ 2, PPh3] ppm. 1H NMR
(CDCl3): 7.98e7.00 [m, Ph þ C6H4, 36H], 6.76 [d, im-CH, 1H,
J ¼ 2.0 Hz], 6.28 [d, C6H4, 2H, J ¼ 7.2 Hz], 6.22 [m, 1H, Ph], 5.52 [br,
im-CH, 1H], 4.27 [m, RuCHCH2Ph, 1H], 2.77 [m, RuCHCH2Ph,
2H] ppm. Anal. Calc. for C55H44Cl4N2O2P2SRu2: C 54.92; H 3.69; N
2.33; Found: C, 55.01; H, 3.65; N, 2.37.
3.5. X-ray diffraction measurements
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Instruments Inc., Madison, WI, 1998.
[31] G.M. Sheldrick, SHELXTL Software Reference Manual, Version 5.1, Bruker AXS
Inc., Madison, WI, 1997.
Intensity data were collected on a Bruker SMART APEX 2000
CCD diffractometer using graphite-monochromated Mo
Ka
radiation (
l
¼ 0.71073 Å). The collected frames were processed
with the software SAINT [29]. The data were corrected for
absorption using the program SADABS [30]. Structures were
solved by direct methods and refined by full-matrix least-
squares on F2 using the SHELXTL software package [31,32].
All non-hydrogen atoms were refined anisotropically. The posi-
tions of all hydrogen atoms were generated geometrically
(Csp3eH ¼ 0.96, Csp2eH ¼ 0.93), assigned isotropic thermal
parameters, and allowed to ride on their respective parent
carbon or oxygen atoms before the final cycle of least-squares
refinement. One phenyl in 3c$CH2Cl2 was isotropically refined
due to disorder. Crystallographic data and experimental details
for 3a$0.5C6H12, 3b$0.5C6H12, 3c$CH2Cl2 and 4a$CH2Cl2 are
given in Table 1.
[32] G.M. Sheldrick, Acta Crystallogr. A 64 (2008) 112e122.