Carbonyl complexes of ruthenium(II) with unsymmetrical phosphine-phosphinesulfide ligands of the type Ph2P(CH2)nP(S)Ph2, n = 1-4

Article abstract of DOI:10.1016/S0277-5387(03)00371-1

Reaction of [Ru(CO)₂Cl₂]_n, with ligands Ph₂P(CH₂)_n P(S)Ph₂ (n = 1(a), 2(b), 3(c), 4(d)) in 1:1 molar ratio produces complex cis[Ru(CO)₂Cl₂(P∩S)](1a) (P∩S = η²-(P, S) coordinated) and cis-[Ru(CO)₂Cl₂(P-S)](1b-d) (P-S = η¹-(P) coordinated), while 1:2 molar ratio yields complex of the type cis-[Ru(CO)₂Cl₂(P-S)₂](2a-d). The complex 2a undergoes partial decarbonylation reaction in CH₂Cl₂-hexane solution to give a new chelated complex [Ru(CO)Cl(P∩S)₂] Cl(2a′). Abstraction of halide with AgClO₄ from the non-chelated complexes 1b-d and 2a-d afford corresponding chelated complexes [Ru(CO)₂Cl(P∩S)](ClO₄)(3b-d) and [Ru(CO)₂(P∩S)₂](ClO₄)₂(4a-d). The molecular structure of the complex 2aκ has been determined by single crystal X-ray diffraction. The ruthenium atom is at the centre of slightly distorted octahedral structure having the two phosphorus atoms of the two chelated P, S coordinated ligands at trans to each other, one CO group and Cl atom completing the coordination sphere. Other complexes have been characterized by elemental analysis, IR, ¹H and ³¹P {H} NMR spectroscopy.

Full text of DOI:10.1016/S0277-5387(03)00371-1

Polyhedron 22 (2003) 2725ꢀ2730
/
www.elsevier.com/locate/poly
Carbonyl complexes of ruthenium(II) with unsymmetrical
phosphineꢀphosphinesulfide ligands of the type Ph2P(CH2)nP(S)Ph2,
nꢁ1ꢀ
/
/
/
4
Pratap Chutia a, Manab Sharma a, Pankaj Das a, Nandini Kumari a,
John Derek Woollins b, Alexandra M.Z. Slawin b, Dipak Kumar Dutta a,*
a Material Science Division, Regional Research Laboratory (CSIR), Jorhat 785006, Assam, India
b Department of Chemistry, University of St. Andrews, St. Andrews KY 16 9ST, UK
Received 5 May 2003; accepted 26 May 2003
Abstract
Reaction of [Ru(CO)2Cl2]n with ligands Ph2P(CH2)nP(S)Ph2 (nꢁ
[Ru(CO)2Cl2(PS S)](1a) (PS Sꢁ
h2-(P, S) coordinated) and cis-[Ru(CO)2Cl2(Pꢀ
molar ratio yields complex of the type cis-[Ru(CO)2Cl2(PꢀS)2](2aꢀd). The complex 2a undergoes partial decarbonylation reaction
in CH2Cl2ꢀhexane solution to give a new chelated complex [Ru(CO)Cl(PS S)2]Cl(2a?). Abstraction of halide with AgClO4 from the
non-chelated complexes 1bꢀ and 2aꢀ afford corresponding chelated complexes [Ru(CO)2Cl(PS S)](ClO4)(3bꢀd) and
[Ru(CO)2(PS S)2](ClO4)2(4aꢀd). The molecular structure of the complex 2a? has been determined by single crystal X-ray
/
1(a), 2(b), 3(c), 4(d)) in 1:1 molar ratio produces complex cis-
/
/
/
/
S)](1bꢀd) (PꢀSꢁ
/
/
/
h1-(P) coordinated), while 1:2
/
/
/
/
/d
/d
/
/
/
/
diffraction. The ruthenium atom is at the centre of slightly distorted octahedral structure having the two phosphorus atoms of the
two chelated P, S coordinated ligands at trans to each other, one CO group and Cl atom completing the coordination sphere. Other
1
complexes have been characterized by elemental analysis, IR, H and 31P {H} NMR spectroscopy.
# 2003 Elsevier Ltd. All rights reserved.
Keywords: Ruthenium(II) carbonyl complexes; Phosphineꢀ/phosphinesulfide; Bidentate chelating ligand; X-ray crystal structures; Octahedral
structures; Steric effect
1. Introduction
ligands is that they contain two non-equivalent phos-
phorus atoms possessing cis coordination donor sites
[7,8]. Hence, the complexes of such ligands allow for the
The coordination chemistry of unsymmetrical chelat-
ing phosphineꢀphosphineoxide (P, O) ligands has got
considerable interest because of their structural novelty
and catalytic applicability [1ꢀ5]. Due to the presence of
two different types of donor sites in the ligands they are
capable of coordinating either as a monodentate (h1-(P)
coordinated) or bidentate chelating (h2-(P, O) coordi-
nated) fashion depending upon the central metal atom
and its environment [3,6]. One more advantage of such
direct measurement of phosphorusꢀphosphorus cou-
/
/
pling constant (2JPÃP) which is very much important in
respect of geometry investigation of the complexes.
/
Literature survey reveals that, phosphineꢀphosphine-
/
sulfide (P, S) ligands have got less attention, despite the
chemistry of such ligands is as potentially interesting as
that of P, O donors ligands. Though a few platinum
metal complexes of such P, S ligands have appeared in
literature [3,5,6,9ꢀ11] but to the best of our knowledge,
/
only one ruthenium complex, [(h6-C6Me6)RuCl2{h1-
PPh2CH2P(S)Ph2}] has so far been reported [9].
* Corresponding author. Tel.: ꢂ
/
91-376-237-0121; Fax: ꢂ91-376-
/
In this paper we report synthesis, spectroscopic
characterization including one X-ray crystal structure
of a complex and reactivity of some ruthenium(II)
237-0011.
E-mail addresses: j.d.woollins@st-andrews.ac.uk (J.D. Woollins),
dipakkrdutta@yahoo.com (D.K. Dutta).
0277-5387/03/$ - see front matter # 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/S0277-5387(03)00371-1

2726
P. Chutia et al. / Polyhedron 22 (2003) 2725ꢀ2730
/
carbonyl complexes of phosphineꢀ
gands with an ultimate aim to use them as catalyst
precursor for organic synthesis.
/
phosphinesulfide li-
2.1.3. [Ru(CO)2Cl(PS
[Ru(CO)2(PS S)2](ClO4)2 (4aꢀ
0.0228 mmol of 1bꢀd and 0.0114 mmol of 2aꢀd were
/
S)]ClO4 (3bꢀ
/
d) and
/
/
d)
/
/
dissolved in 10 cm3 dichloromethane and to each of
these 10 cm3 methanol solution of 0.0228 mmol AgClO4
was added. The reaction mixtures were refluxed under
nitrogen for 3 h. The dirty white precipitate of silver
chloride (AgCl) was filtered off and the light yellow
filtrate was evaporated to dryness under vacuum to get a
light yellow solid. The solid compounds were washed
with methanol followed by diethyl ether. The complexes
were recrystallized from acetone.
2. Experimental
All the solvents used were distilled under nitrogen
prior to use. Carbon and hydrogen analyses were done
on a Perkinꢀ
analyses were performed by standard analytical method
[12]. FT-IR spectra of range 4000ꢀ
400 cmꢃ1 and 400ꢀ
200 cmꢃ1 were recorded using Perkinꢀ
Elmer 2000 and
PerkinꢀElmer 883 spectrophotometer, respectively, in
/Elmer 2400 elemental analyzer. Chloride
/
/
/
Analytical data and physical properties of complexes
are shown in Table 1.
/
KBr disc. NMR data were recorded on a Bruker DPX
300 MHz spectrometer and the 1H and 31P NMR
chemical shifts were quoted relative to SiMe4 and 85%
H3PO4 as internal and external standard, respectively,
using CDCl3 and d6-acetone as solvent. Melting points
were determined with a BUCHI B-540 apparatus.
2.2. X-ray crystallography
A suitable crystal of the complex 2a? for X-ray
diffraction study was developed from a CH2Cl2ꢀhexane
solution. The crystal data and structure refinement for
the complex are given in Table 2.
/
RuCl3×
Ltd, Kolkata, India. Analytically pure Ph2P(CH2)nPPh2
(nꢁ1ꢀ4) and elemental sulfur were purchased from M/
/3H2O was purchased from M/S Arrora Matthey
/
/
S Aldrich, USA and used without further purification.
The ligands, Ph2P(CH2)nP(S)Ph2 were prepared by
refluxing a solution of Ph2P(CH2)nPPh2 in benzene
with one molar equivalent of elemental sulfur for 3 h
under nitrogen and purified by chromatographic tech-
niques. The starting complex [Ru(CO)2Cl2]n was pre-
3. Results and discussion
Reaction of [Ru(CO)2Cl2]n with equimolar quantity
of the ligand a gives octahedral six-coordinated complex
cis-[Ru(CO)2Cl2(PS S)](1a) (Scheme 1). In the complex
/
pared by following literature method [13ꢀ
/16].
1a, the two terminal carbonyl groups are cis to each
other as they show two almost equally intense n(CO)
2.1. Synthesis of metal complexes
bands at 1994 and 2066 cmꢃ1 (Table 3) [17ꢀ
/
19]. The
n(PS) band occurs at 576 cmꢃ1 which is about 30 cmꢃ1
lower than that of the free ligand (n(PS)ꢁ
606 cmꢃ1
2.1.1. [Ru(CO)2Cl2(PS
/
S)](1a) and
/
)
[Ru(CO)2Cl2(PꢀS)](1bꢀ
/
/
d)
indicating chelation via metal sulfur bond formation
[3,9]. The presence of only one n(RuCl) band at ca. 351
cmꢃ1 in 1a indicates two chlorides are mutually trans to
each other [20,21]. The 1H NMR spectra (Table 3) of 1a
0.0877 mmol of [Ru(CO)2Cl2]n was dissolved in 10
cm3 methanol and to this 0.0877 mmol of corresponding
ligand aꢀ
d in 10 cm3 dichloromethane was added. The
/
reaction mixture was stirred at room temperature for
about 2 h and the solvent was evaporated under vacuum
to produce a yellow compound. The compound so
obtained was washed with diethyl ether and recrystal-
lized from dichloromethane solution.
show two multiplet resonances in the range d 7.12ꢀ
/
7.40
and d 7.62ꢀ8.13 ppm attributed to two non-equivalent
/
phenylic protons and a doublet of doublet signal at d
3.79 ppm for methylene protons. The chelate formation
in 1a is further corroborated by a 0.44 ppm down field
shift of the methylene protons compared to the free
ligand. The 31P {H} NMR spectra (Table 3) exhibit two
distinct doublet resonances at d 40.9 and 57.8 ppm for
tertiary phosphorus (P1) and pentavalent phosphorus
(P2), respectively [5]. As compared to the free ligand, the
P1 and P2 atoms show a down field shift of d 63.6 and
12.6 ppm, respectively, which is in good agreement with
the chelate formation in complex 1a [6,22]. The observed
2.1.2. [Ru(CO)2Cl2(Pꢀ
0.031 mmol of complex 1aꢀ
dichloromethane and to this 0.031 mmol of correspond-
ing ligand aꢀ
d in 10 cm3 dichloromethane was added. A
yellow compound was obtained following the same
reaction condition used for the complex 1aꢀd. After
/
S)2] (2aꢀ
/
d)
/
d was dissolved in 10 cm3
/
/
washing with diethyl ether the complexes were recrys-
tallized from dichloromethane solution. The complex
2
low JPÃP value of 76.3 Hz indicates that phosphorus
2aꢀ
mmol of [Ru(CO)2Cl2]n in 10 cm3 MeOH solution with
0.0877 mmol of ligands aꢀ
d in 10 cm3 dichloromethane
solution.
/
d could be synthesized directly by treating 0.0439
and sulfur atoms of the ligand coordinated to the metal
atom in the complex 1a are cis to one another [20,23].
Thus on the basis of IR and NMR data the most
probable structure of 1a is shown in Figure A.
/

P. Chutia et al. / Polyhedron 22 (2003) 2725ꢀ
/2730
2727
Table 1
Analytical data and physical properties of complexes
Complex
Yield (%)
Melting point (8C)
Elemental analysis found (Calc.) in %
C
H
Cl
1a
1b
1c
1d
2a
2b
2c
2d
3b
3c
3d
4a
4b
4c
4d
93
97
96
96
98
97
97
98
86
89
90
90
89
86
86
85 (dec.)
206
217
50.21 (50.27)
51.01 (51.03)
51.80 (51.74)
52.50 (52.44)
58.86 (58.82)
59.46 (59.51)
60.13 (60.16)
60.73 (60.78)
46.47 (46.51)
47.28 (47.25)
47.91 (47.96)
52.56 (52.49)
53.31 (53.25)
53.94 (53.98)
54.73 (54.67)
3.44 (3.41)
3.60 (3.64)
3.84 (3.87)
4.02 (4.08)
4.12 (4.15)
4.38 (4.41)
4.68 (4.66)
4.83 (4.89)
3.29 (3.32)
3.50 (3.53)
3.70 (3.73)
3.68 (3.70)
3.92 (3.94)
4.15 (4.18)
4.36 (4.40)
10.94 (11.02)
10.76 (10.78)
10.51 (10.56)
10.39 (10.34)
6.65 (6.69)
6.49 (6.52)
6.33 (6.36)
6.24 (6.20)
4.88 (4.91)
4.80 (4.82)
4.71 (4.73)
229
90 (dec.)
248
257
248
160
178
181
148
153
ꢀ/
ꢀ/
ꢀ/
ꢀ/
183
100
Table 2
Crystal data and structure refinement for the complex 2a?
Empirical formula
Formula weight
Temperature (K)
C51.50H45Cl3OP4RuS2
1075.29
125(2)
0.71073
monoclinic
P21/n
˚
Wavelength (A)
Crystal system
Space group
˚
a (A)
13.062(6)
20.739(10)
19.689(10)
90
˚
b (A)
˚
c (A)
a (8)
b (8)
g (8)
107.259(8)
90
3
˚
V (A )
Z
5093(4)
4
1.402
Chart 1.
Dcalc (Mg mꢃ3
)
Absorption coefficient (mmꢃ1
F(0 0 0)
)
0.709
2196
In contrast to the ligand a, the reaction of the ligand
bꢀd with [Ru(CO)2Cl2]n in one molar equivalent ratio
produces 16 election five-coordinated non-chelated
complex cis-[Ru(CO)2Cl2(PꢀS)] (1bꢀd). Similar type of
five-coordinated complexes were also reported earlier
/
Crystal size (mm)
u Range for data collection
Index ranges
12ꢄ
2.21ꢀ
115
235
21019
/
1ꢄ
25.08
h 5
l 516
/
01
/
/
/
ꢃ
ꢃ/
/
/
/
15, ꢃ
/
225
/
k 524,
/
/
/
[24]. In case of complex 1bꢀ
d, h1-(P) coordination is
/
Reflections collected
favoured over h2-(P, S) coordination mode though the
latter could lead to a more favourable 18 electron
complex. It may be attributed to the fact that the h2-
(P, S) coordination would lead to six, seven and eight
member rings which are unfavourable due to high ring
strain [25]. Similar to complex 1a, two equally intense
Independent reflections
8469 [Rint
93.6%
ꢁ/0.1931]
Completeness to uꢁ25.088
/
Absorption correction
Max. and min. transmission
Refinement method
multiscan
1.00000 and 0.521595
full-matrix least-squares on
F2
Data/restraints/parameters
Goodness-of-fit on F2
8469/0/572
0.936
terminal n(CO) bands of the complex 1bꢀ
range 1993ꢀ
2071 cmꢃ1 due to two cis carbonyl groups.
The n(PS) band occurs almost in the same position as
that of corresponding free ligand bꢀ
d suggesting h1-(P)
coordination mode of the ligand. The observed single
352 cmꢃ1 is consistent
/d appear in the
Final R indices [I ꢀ
/
2s(I)]
R1ꢁ
R1ꢁ
0.743 and ꢃ
/
0.1111, wR2ꢁ
0.3072, wR2ꢁ
0.522
/0.1860
/
R indices (all data)
/
/0.2599
Largest difference peak and hole
ꢃ3
/
/
˚
(e A
)
n(RuCl) band in the range 345ꢀ
/
Similar to the complex 1a, the 31P {H} NMR spectra of
1bꢀd also show two doublet resonances, one relatively
high field at around d 23ꢀ34 ppm for the P1 atom and
with mutually trans disposition of the chlorides. The 1H
NMR spectra of this complex show characteristics
resonance (Table 3) for phenylic and methylene protons.
/
/

2728
P. Chutia et al. / Polyhedron 22 (2003) 2725ꢀ2730
/
Table 3
2
IR, 31P {H} and 1H values (d in ppm; JPÃP in Hz) of the complexes
Complex
IR (cmꢃ1
)
31P {H} NMR
1H NMR
C6H5
n(CO)
n(PS)
n(RuCl)
dP
dPÄS
2JPÃP
Ã
/
(CH2)n Ã
/
1a
1b
1c
1d
2a
2b
2c
2d
3b
3c
3d
4a
4b
4c
4d
1994, 2066
1995, 2066
1993, 2071
1995, 2067
1990, 2067
1995, 2066
1993, 2070
1993, 2071
1996, 2067
1997, 2065
1992, 2069
1994, 2062
1992, 2066
1999, 2068
1991, 2063
576
614
612
613
607
613
611
614
574
580
580
577
575
579
582
351
352
348
345
347
360
340
345
346
352
359
40.9d
23.0d
33.8d
33.5d
24.4d
26.6d
37.7d
19.9d
45.0d
44.0d
48.7d
37.7d
41.6d
44.1d
47.1d
57.8d
46.4d
49.9d
43.3d
41.2d
46.5d
47.2d
43.2d
55.7d
54.8d
57.9d
64.5d
52.2d
56.2d
46.3d
76.3
65.6
66.9
44.8
71.9
67.4
41.3
77.5
41.9
45.7
49.8
46.2
58.1
54.2
57.2
7.12ꢀ
7.05ꢀ
7.26ꢀ
7.34ꢀ
7.20ꢀ
7.06ꢀ
7.26ꢀ
7.24ꢀ
7.49ꢀ
7.54ꢀ
7.48ꢀ
7.27ꢀ
7.53ꢀ
7.45ꢀ
7.40ꢀ
/
7.40m, 7.62ꢀ
7.46m, 7.77ꢀ
7.47m, 7.73ꢀ
7.52m, 7.72ꢀ
7.44m, 7.65ꢀ
7.46m, 7.67ꢀ
7.47m, 7.74ꢀ
7.46m, 7.72ꢀ
7.62m, 7.70ꢀ
7.72m, 7.81ꢀ
7.59m, 7.73ꢀ
7.62m, 7.71ꢀ
7.66m, 7.68ꢀ
7.66m, 7.81ꢀ
7.70m, 7.82ꢀ
/
8.13m
8.47m
7.83m
7.86m
8.03m
8.29m
8.04m
7.89m
7.94m
8.10m
8.00m
8.12m
8.01m
7.98m
7.95m
3.79dd
/
/
2.72m, 3.12m
2.65m, 1.65m
2.48m, 2.05m
3.62dd
/
/
/
/
/
/
/
/
2.74m, 3.43m
2.56m, 1.63m
2.45m, 2.03m
3.21m, 4.01m
3.26m, 2.89m
3.19m, 2.99m
3.80dd
/
/
/
/
/
/
/
/
/
/
ꢀ/
ꢀ/
ꢀ/
ꢀ/
/
/
/
/
3.30m, 3.96m
3.14m, 2.85m
3.12m, 2.96m
/
/
/
/
Free ligand (aꢀ
/
d): IR: n(PS): 606(a), 614(b), 612(c), 614(d); 31P NMR: dP and dPÄS: ꢃ
(CH2)n Ã: 3.35dd(a); 2.62m, 2.90m(b); 2.52m, 1.35m(c); 2.40m, 2.00m(d). d: Doublet; m: multiplet; dd: doublet of doublet.
/
22.7, 45.2d (a); ꢃ
/
16.8, 42.6d(b); ꢃ
/
13.2, 47.1d(c); ꢃ15.5,
/
43.1d(d); 1H NMR: Ã
/
pyramidal arrangement (Figure B) seems to be better
possibility than the trigonal bipyramidal structure [24].
Reaction of 1aꢀ
corresponding ligand aꢀ
dral complex [Ru(CO)2Cl2(Pꢀ
The complex 2aꢀd can also be prepared directly by
treating [Ru(CO)2Cl2]n with ligand aꢀd in 1:2 molar
ratio. The complex 2aꢀd exhibit n(PS) band almost in
the same position as that of corresponding free ligand
(Table 3) suggesting phosphineꢀphosphinesulfide ligand
/
d with one molar equivalent of
d yields six-coordinated octahe-
S)2](2aꢀd) (Scheme 1).
/
/
/
/
/
/
/
is coordinated to the metal through the tertiary phos-
phorus atom only. The position and nature of n(CO)
and n(RuCl) bands in the IR spectrum (Table 3) is well
agreed with the mutual cis disposition of the terminal
CO groups and trans disposition of the chlorides. The
1H NMR spectra of 2aꢀ
multiplet resonances for phenylic protons at around d
7.06ꢀ7.47 and d 7.65ꢀ8.29 ppm in addition to methyl-
ene protons resonances. Similar to the complex 1aꢀd,
the 31P {H} NMR spectra of 2aꢀ
d show two doublet
resonances at around d 19ꢀ38 and d 41ꢀ48 ppm due to
/
d show two characteristics
/
/
/
/
/
/
Scheme 1.
2
P1 and P2 atom, respectively. The low JPÃP values
(Table 3) suggest that the two tertiary phosphorus
atoms of the two ligands are mutually cis to one another
[20,23]. Thus, Figure C is the most probable structure of
other low field at around d 43ꢀ
The large down field shift of about 39ꢀ
/
50 ppm for the P2 atom.
/49 ppm
compared to the free ligand for the P1 atom is consistent
with the monodentate nature of the ligand. Theoreti-
complex 2aꢀ
Abstraction of halide from non-chelated complex 1bꢀ
d and 2aꢀd by one and two molar equivalents of
AgClO4, respectively, lead to chelated complex
[Ru(CO)2Cl(PS S)]ClO4 (3bꢀd) and [Ru(CO)2(PS
S)2](ClO4)2 (4aꢀd) (Scheme 1). In the complex 3bꢀ
and 4aꢀd, the n(PS) band appears in the range 574ꢀ582
cmꢃ1 which is 29ꢀ40 cmꢃ1 lower compared to the
/
d.
/
cally, the five-coordinated complex 1bꢀd could have two
/
/
geometrical arrangements, either a square pyramidal or
trigonal bipyramidal structure. Thus, on the basis of
spectroscopic evidences (IR and NMR) only, the
possibility of the two structures can not be distin-
guished. However, on steric point of view, the square
/
/
/
/
/
d
/
/
/

P. Chutia et al. / Polyhedron 22 (2003) 2725ꢀ
/2730
2729
corresponding non-chelated complex 1bꢀ
/
d and 2aꢀd
/
indicating h2-(P, S) coordination mode of the ligand.
Similar to other complex, the IR spectra show char-
acteristics bands for cis carbonyl groups. In addition,
the IR spectra also show two new bands in the range
1087ꢀ
ClO4ꢃ anion [9,26,27]. The chelate formation in 3bꢀ
and 4aꢀ
d can also be substantiated from the 31P {H}
/
1099 cmꢃ1 and 620ꢀ
/
628 cmꢃ1 for uncoordinated
/
d
/
NMR spectra (Table 3) where a large down field shift is
observed for both the tertiary and pentavalent phos-
2
phorus atoms. The JPÃP values are consistent with
mutual cis arrangement of the phosphorus and sulfur
atoms in 3bꢀ
/
d and two phosphorus atoms in 4aꢀd,
/
respectively. The 1H NMR spectra of the complexes
show characteristics resonance for phenylic and meth-
ylene protons. Similar to the five-coordinated complex
1bꢀ
/
d, the complex 3bꢀd would also be expected to have
/
a square pyramidal geometry and the most probable
structure is shown in Figure D. Again, similar to the
Fig. 1. Crystal structure of [Ru(CO)Cl{Ph2PCH2P(S)Ph2}2]Cl(2a?).
other six coordinated octahedral complexes 1a, 2aꢀ
the most probable structure of complex 4aꢀd is shown
in Figure E.
It is interesting that the dicarbonyl complex 2a on
storing in CH2Cl2ꢀhexane solution for about 15 days
undergoes a partial decarbonylation reaction resulting a
monocarbonyl chelated complex [Ru(CO)Cl(PS S)2]Cl
(2a?) (Scheme 2) as indicated by a single terminal n(CO)
band at 1969 cmꢃ1. Such decarbonylation reaction was
also observed in rhodium a-(2-furyl)-N-phenylnitrone
complex [28]. The two dangling P, S coordinated ligands
undergo chelation which is corroborated by the shifting
of free n(PS) band at 606 to 577 cmꢃ1. In order to
obtain an unambiguous characterization of the complex
2a?, an X-ray diffraction study was undertaken. The
arrangement of the atoms in the crystal are shown in the
Fig. 1 and some important bond angles and bond
lengths are listed in Table 4. In the molecule, Ru(II) is
situated at the centre of a slightly distorted octahedral
coordination environment with two chelated P, S
coordinated ligands, one CO group and one Cl atom.
Due to the strong trans effect, both the phosphorus
atoms are mutually trans to each other and hence the
/
d,
/
Table 4
˚
Selected bond lengths (A) and bond angles (8) of the complex 2a?
/
Bond lengths
Ru(1)Ã
Ru(1)Ã
Ru(1)Ã
Ru(1)Ã
Ru(1)Ã
Ru(1)Ã
/
C(61)
P(2)
P(4)
S(3)
1.859(17)
2.341(4)
2.353(4)
2.386(4)
2.451(4)
2.403(4)
/
/
/
/
/S(1)
/Cl(1)
Bond angles
C(61)ÃRu(1)Ã
C(61)ÃRu(1)Ã
P(2)ÃRu(1)Ã
C(61)Ã
P(2)ÃRu(1)Ã
P(4)ÃRu(1)Ã
C(61)Ã
P(2)ÃRu(1)Ã
P(4)ÃRu(1)Ã
S(3)ÃRu(1)Ã
C(61)ÃRu(1)Ã
P(2)ÃRu(1)Ã
P(4)ÃRu(1)Ã
S(3)ÃRu(1)Ã
Cl(1)ÃRu(1)Ã
/
/
P(2)
93.1(5)
91.3(5)
/
/P(4)
/
/
P(4)
175.54(16)
89.7(6)
/
Ru(1)Ã
/S(3)
/
/
S(3)
S(3)
89.35(14)
90.96(14)
92.6(5)
/
/
/
Ru(1)Ã
/Cl(1)
/
/
Cl(1)
85.08(14)
94.43(14)
174.06(14)
175.9(6)
90.68(13)
84.86(14)
91.73(15)
86.29(15)
/
/
Cl(1)
/
/
Cl(1)
/
/S(1)
/
/
S(1)
S(1)
/
/
/
/
S(1)
complex is apparently preferred. The RuÃ
distances are within the range of values typical for
Ru(II) complexes [29,30]. The RuÃS(1) distance is
S(3) and the weakening of the
/
Cl and RuÃ
/P
/
/
S(1)
/
slightly larger than RuÃ
/
bond in the former results from the stronger trans
influence of the CO group compared to Cl atom. The
bond angles for S(3)ÃRuÃCl, P(2)ÃRuÃP(4) and
C(61)ÃRuÃS(1) are 174.068, 175.548 and 175.908, re-
/
/
/
/
/
/
spectively, and are therefore slightly deviated from 1808.
This deviation is probably due to steric effect of the
bulky phenyl rings. In the five member chelate rings, the
angles P(4)Ã
/
RuÃ
/
S(3) and P(2)Ã
/
RuÃS(1) are 90.968 and
/
90.688, respectively, and the slight deviation from 908 is
probably due to strain of five member ring [29].
Scheme 2.

2730
P. Chutia et al. / Polyhedron 22 (2003) 2725ꢀ2730
/
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4. Supplementary material
Supplementary data are available from the CCDC, 12
Union Road, Cambridge CB2 1EZ, UK on request.
CCDC deposition number 208116. Copies of this
information may be obtained free of charge from The
Director, CCDC, 12 Union Road, Cambridge, CB2
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The authors are grateful to the Director, Regional
Research Laboratory (CSIR), Jorhat, India, for his kind
permission to publish the work. The authors thank Dr
P.C. Borthakur, Head Material Science Division, RRL
Jorhat, for his encouragement and support. The Depart-
ment of Science and Technology (DST) New Delhi and
Oil Industry Development Board (OIDB), Ministry of
Petroleum & natural Gas, New Delhi, are acknowledged
for their partial financial grant. The authors P. Das and
N. Kumari thank CSIR, New Delhi, for the award of
Senior Research Fellowship (SRF).
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