Allyl functionalized phosphinite and phosphonite ligands: Synthesis, transition metal chemistry and orthopalladation reactions

Article abstract of DOI:10.1007/s12039-012-0279-4

Allyl functionalized phosphinite PPh₂(OAr) [Ar=C ₆H₄(o-C₃H₅)] (1) and phosphonite PPh(OAr)₂ (2) ligands were prepared by the reactions of 2-allylphenol with PPh₂Cl and PPhCl

Full text of DOI:10.1007/s12039-012-0279-4

c
J. Chem. Sci. Vol. 124, No. 4, July 2012, pp. 773–779. ꢀ Indian Academy of Sciences.
Allyl functionalized phosphinite and phosphonite ligands: Synthesis,
transition metal chemistry and orthopalladation reactions
SINGAPPAGUDEM GOVINDARAJUa, GUDDEKOPPA S ANANTHNAGa, SUSMITA NAIKa,
SHAIKH M MOBINb and MARAVANJI S BALAKRISHNAa,∗
aPhosphorus Laboratory, Department of Chemistry, Indian Institute of Technology Bombay,
Mumbai 400 076, India
bNational Single Crystal X-ray Diffraction Facility, Indian Institute of Technology Bombay,
Mumbai 400 076, India
e-mail: krishna@chem.iitb.ac.in
MS received 28 December 2011; accepted 29 February 2012
Abstract. Allyl functionalized phosphinite PPh2(OAr) [Ar = C6H4(o-C3H5)] (1) and phosphonite PPh(OAr)2
(2) ligands were prepared by the reactions of 2-allylphenol with PPh2Cl and PPhCl2, respectively. The ruthe-
nium(II) complexes, [Ru(η6-p-cymene)(PPh2(OAr))Cl2] (3) and [Ru(η6-p-cymene)(PPh(OAr)2Cl2)] (4) were
obtained by reacting 1 or 2 with [Ru(η6-p-cymene)Cl2]2 in 2:1 molar ratios, respectively. Reactions of 1 or 2
with AuCl(SMe2) gave [Au{PPh2(OAr)}Cl] (5) or [Au{PPh(OAr)2}Cl] (6) in good yield. The palladium com-
plex, [Pd{PPh(OAr)2}2Cl2] (7) was prepared by reacting Pd(COD)Cl2 with 2 in 1:2 molar ratio. The reaction
between Pd(COD)Cl2 and 1 yielded a mixture of orthopalladated cis- and trans-[Pd(Ph2P(OAr))Cl]2 (8a and
8b). The treatment of 8 with PPh3 and Ph2PCH2PPh2 resulted in the cleavage of chloro bridge to give respec-
tively, [Ph2(OAr)PPd(PPh3)Cl] (9) and [Ph2(ArO)PPd(η2-dppm)]OTf (10). Single crystal X-ray structure of
the ruthenium complex 3 is described.
Keywords. Phosphonites; palladium(II); orthopalladation; orthometallation; metal complexes; gold(I) and
ruthenium(II) complexes.
1. Introduction
metal chemistry and orthopalladation reactions of olefin
functionalized phosphinite and phosphonite ligands.
Phosphinite-metal complexes have become the most
popular catalysts for several organic transformations
because of their catalytic potential, easier synthetic
methods and versatile coordination behaviour.1 Orthopal-
ladated phosphinite complexes attracted much atten-
tion because of their excellent activity in C–C and
C–N couplings reactions.2,3 Several methods have been
employed for the preparation of palladacycles, the pre-
eminent ones being, the C–H bond activation, oxida-
tive addition of C–X or C–C bonds, transmetallation
and addition of unsaturated bonds. The formation of
palladacycles from phosphinite ligands is facile. The
palladacycles contain carbon–palladium bond formed
by an aromatic C–H activation (ortho-activation).4 The
majority of palladacycles contain one σ (Pd–Csp2) bond
and a coordinate bond via donor atom to form five-
or six-membered metallacycles. Stable palladacycles
usually contain five-membered rings. Larger rings are
less stable as they often facilitate reductive elimina-
tion.5 In this paper, we describe the synthesis, transition
2. Experimental
All experimental manipulations were performed under
an inert atmosphere of dry nitrogen or argon, using
standard Schlenk techniques. All the solvents were
purified by conventional procedures and distilled prior
to use.6 [Pd(COD)Cl2],7 [Ru(η6-cymene)Cl2]2,8 and
[AuCl(SMe2)]9 were prepared according to the pub-
lished procedures. Other reagents were obtained from
commercial sources and used after purification. The
1H NMR and 31P{1H} NMR (δ in ppm) spectra were
recorded in Bruker AV 400 spectrometer operating at
400 and 162 MHz, respectively. TMS and 85% H3PO4
1
were used as internal and external standard for H
and 31P{1H} NMR, respectively. All the spectra were
recorded in CDCl3 solutions with CDCl3 as internal
lock; positive shifts lie downfield of the standard in all
of the cases. The microanalyses were performed using a
Carlo Erba Model 1112 elemental analyzer. Mass spec-
tra were recorded using Waters Q-Tof micro (YA-105).
∗For correspondence
773

774
Singappagudem Govindaraju et al.
The melting points were observed in capillary tubes and (s, CH3, 3H), 0.70 (d, 3 JHH = 7 Hz, CH3, 6H). 31P{1H}
are uncorrected.
NMR (162 MHz, CDCl3): δ 113.6 (s). MS (EI): m/z =
589.2 (M-Cl).
2.1 Synthesis of PPh2(OAr) [Ar = C6H4(o-C3H5)] (1)
2.4 Synthesis of [Ru(η6-p-cymene)Cl2{PPh(OAr)2}]2 (4)
A solution of chlorodiphenylphosphine (1.4 mL 1.72 g,
7.68 mmol) in diethyl ether (20 mL) was added drop-
wise to a mixture of 2-allylphenol (1 mL, 1.03 g,
7.68 mmol) and triethylamine (1.1 mL, 0.8 g, 7.8 mmol)
also in diethyl ether (20 mL) under constant stirring at
0 ◦C. The reaction mixture was allowed to warm to room
temperature and stirred for 12 h. The amine hydrochlo-
ride salt thus formed was filtered through a frit contain-
ing celite. All volatiles were removed under vacuum
This was synthesized by a procedure similar to that
of 3, using 2 (0.04 g, 0.108 mmol) and [Ru(η6-p-
cymene)Cl2] (0.033 g, 0.054 mmol). Yield: 83% (0.064 g).
◦
Mp: 180–184 C. Anal. Calcd for C34H37Cl2O2PRu:
1
C, 60.00; H, 5.48. Found: C, 59.20; H, 5.20. H NMR
(400 MHz, CDCl3): δ 7.90–7.03 (m, ArH, 13H), 6.03
3
(m, CH, 2H), 5.41 (d, JHH = 6.4 Hz, CH2, 2H), 5.25
(d, 3 JHH = 6.4 Hz, CH2, 2H), 5.16–5.10 (m, CH2, 4H),
1
to give 1 as a colourless liquid. Yield: 90% (2.2 g). H
3
3.65 (m, CH2, 4H), 2.73 (m, JHH = 7 Hz, CH, 1H),
NMR (400 MHz, CDCl3): 7.62–6.94 (m, ArH, 14H),
3
1.74 (s, CH3, 3H), 1.02 (d, JHH = 7 Hz, CH3, 6H).
5.96 (m, CH, 1H), 4.90 (m, CH2, 2H), δ 3.41 (d, 3 JHH
=
31P{1H} NMR (162 MHz, CDCl3): δ 141.6 (s). MS
(EI): m/z = 644.8 (M-Cl).
6.1 Hz, CH2, 2H). 31P{1H} NMR (162 MHz, CDCl3): δ
107.9 (s). MS (EI): m/z = 319.2 (M+1).
2.5 Synthesis of Au{PPh2(OAr)}Cl (5)
2.2 Synthesis of PPh(OAr)2 (2)
A solution of AuCl(SMe2) (0.028 g, 0.093 mmol)
in dichloromethane (10 mL) was added drop-wise
to a solution of 1 (0.03 g, 0.093 mmol) also in
dichloromethane (5 mL) at room temperature. The reac-
tion mixture was stirred for 4 h, with minimum expo-
sure to light. Then the solvent was removed under
reduced pressure and product was isolated as a white
To a stirred solution of dichlorophenylphosphine
(1.03 mL, 1.34 g, 7.6 mmol) in diethyl ether, (20 mL)
was added drop-wise to a mixture of 2-allylphenol
(2 mL, 2.06 g, 15.3 mmol) and triethylamine (2.2 mL,
◦
1.61 g, 16 mmol) in the same solvent (20 mL) at 0 C.
The reaction mixture was allowed to warm to room tem-
perature and stirring was continued for another 12 h.
The amine hydrochloride formed was filtered through a
frit containing celite, all volatiles were removed under
reduced pressure to give 2 as a colourless liquid. Yield:
95% (5.4 g). 1H NMR (400 MHz, CDCl3): δ 7.86–6.99
(m, ArH, 13H), 5.88 (m, CH, 2H), 4.96 (m, CH2, 4H),
3.34 (m, CH2, 4H). 31P{1H} NMR (162 MHz, CDCl3):
δ 158.4 (s).
◦
solid. Yield: 85% (0.056 g). Mp: 172–174 C. Anal.
Calcd for C21H19AuClOP: C, 45.80; H, 3.48. Found: C,
1
45.36; H, 3.54. H NMR (400 MHz, CDCl3): δ 7.02–
7.71 (m, ArH, 14H), 5.96 (m, CH, 1H), 4.97 (m, CH2,
2H), 3.42 (d, 3 JHH = 6.1 Hz, CH2, 2H). 31P{1H} NMR
(162 MHz, CDCl3): δ 111.2 (s).
2.6 Synthesis of Au{PPh(OAr)2}Cl (6)
2.3 Synthesis of Ru(η6-p-cymene){PPh2(OAr)}Cl2 (3)
This was synthesized by a procedure similar to that
of 5, using 2 (0.04 g, 0.1068 mmol) and AuCl(SMe2)
(0.03◦15 g, 0.1068 mmol). Yield: 79% (0.051 g). Mp:
168 C (dec). Anal. Calcd for C24H23AuClO2P: C,
A
solution of [Ru(η6-p-cymene)Cl2]2 (0.036 g,
0.058 mmol) in dichloromethane (10 mL) was added
drop-wise to a solution of PPh2(OAr) (0.037 g,
0.116 mmol) in the same solvent (5 mL) at room tem-
perature. The clear red coloured solution thus obtained
was stirred for 4 h. The solvent was removed under
reduced pressure and the product was washed with
pet ether to give 3 as a r◦ed crystalline solid. Yield:
87% (0.065 g). Mp: 145 C (dec). Anal. Calcd for
C31H33Cl2OPRu: C, 59.62; H, 5.33. Found: C, 59.64;
H, 5.11. 1H NMR (400 MHz, CDCl3): δ 7.97–7.02 (m,
ArH, 14H), 6.27 (m, CH, 1H), 5.22 (m, CH2, 2H), 3.80
1
47.50; H, 3.82. Found: C, 48.09; H, 2.79. H NMR
(400 MHz, CDCl3): δ 8.07–7.18 (m, ArH, 13H), 5.79
(m, CH, 2H), 4.96 (m, CH2, 4H), 3.31 (m, CH2, 4H).
31P{1H} NMR (162 MHz, CDCl3): δ 135.1 (s).
2.7 Synthesis of [Pd{PPh(OAr)2}2Cl2] (7)
A solution of [Pd(COD)Cl2] (0.013 g, 0.046 mmol)
in dichloromethane (10 mL) was added drop-wise to
3
(d, JHH = 6.2 Hz, CH2, 2H), 2.51 (m, CH, 1H), 1.58

Phosphinite and phosphonite ligands
775
solution of 2 (0.035 g, 0.92 mmol) in the same sol- (0.026 g, 0.1 mmol) in the same solvent (5 mL) at room
vent (5 mL) at room temperature. The reaction mix- temperature. The reaction mixture was stirred for 4 h,
ture was stirred for 4 h. The solvent was removed under then filtered through celite and the solvent was removed
vacuum, to get the product as a pale yellow solid. under reduced pressure to give 10 as yellow solid.
Yield: 91% (0.039 g). Mp: 156–160 ◦C, Anal. Calcd for Yield: 80% (0.074 g). Mp: 127–130 ◦C. Anal. Calcd for
C48H46Cl2O4P2Pd: C, 62.25; H, 5.01. Found: C, 61.21; C47H40F3O4P3PdS: C, 58.97; H, 4.21. Found: C, 59.13;
1
H, 4.79. 1H NMR (400 MHz, CDCl3): δ 7.89–7.09 (m, H, 4.56. H NMR (400 MHz, CDCl3): δ 7.73–6.66
ArH, 26H), 5.63 (m, CH, 2H), 4.86 (m, CH2, 4H), 3.19 (m, ArH, 33H), 5.98 (m, CH, 1H), 4.65 (m, CH2, 2H),
2
(d, 3 JHH = 6.1 Hz, CH2, 4H). 31P{1H} NMR (162 MHz, 3.19 (m, CH2, 2H), 1.36 (d, JPH = 7 Hz, CH2, 2H).
CDCl3): δ 118.9 (s).
31P{1H} NMR (162 MHz, CDCl3): δ149.7 (dd,2 JPP
=
385 Hz, 18 Hz), −20.8 (dd, 2 JPP = 385 Hz, 63 Hz) and
−25.7 (dd, 2 JPP = 63 Hz, 18 Hz). MS (EI): m/z = 806.7
(M-OTf).
2.8 Synthesis of [Pd{PPh2(OAr)}Cl]2 (8a and 8b)
A solution of [Pd(COD)Cl2] (0.152 g, 0.534 mmol) in
toluene (20 mL) was added to solution of PPh2(OAr)
(1) (0.17 g, 0.536 mmol) also in toluene (20 mL), and
the solution was refluxed for 12 h. The reaction mixture
was allowed to cool to room temperature and filtered
through celite. The solvent was removed under vacuo
to give 8 as a yellow coloured solid. Yield: 80% (0.2 g).
2.11 X-ray crystallography
Single crystal X-ray structural study was performed
on a CCD Oxford Diffraction XCALIBUR-S diffrac-
tometer equipped with an Oxford Instrument with low-
temperature attachment. Data were collected at 150(2)
K using graphite-monochromated Mo–Kα radiation
(γα = 0.71073 Å). The strategy for the data collection
was evaluated by using the CRYSALISPRO CCD soft-
ware. The data were collected by the standard ‘phi-
omega scan’ techniques and were scaled and reduced
◦
Mp: 157–162 C. Anal. Calcd for C42H36Cl2O2P2Pd:
1
C, 54.93; H, 3.95. Found: C, 55.77; H, 2.95. H NMR
(400 MHz, CDCl3): δ 7.66–6.93 (m, ArH, 26H), 5.96
(m, CH, 2H), 5.44 (m, CH2, 4H), 3.30 (m, CH2, 4H).
31P{1H} NMR (162 MHz, CDCl3): δ 151.9 (s) and
151.1 (s). MS (EI): m/z = 882.6 (M-Cl).
Table 1. Crystallographic data for complex 3.
2.9 Synthesis of [Ph2(OAr)PPd(PPh3)Cl] (9a and 9b)
Empirical formula
Fw
crystal system
space group
a, Å
b, Å
c, Å
C31H33Cl2OPRu.CHCl3
743.88
A solution of PPh3 (0.025 g, 0.096 mmol) in toluene
(5 mL) was added to a solution of 8a and 8b (0.041 g,
0.048 mmol) in toluene (10 mL) at room temperature.
The reaction mixture was stirred for 4 h. The solvent
was removed under reduced pressure to give 9 as a
Triclinic
P1
10.3415(3)
10.4132(4)
15.9431(5)
87.380(3)
80.473(2)
76.999(3)
1649.74(9)
2
◦
yellow solid. Yield: 82% (0.057 g). Mp: 159 C (dec).
α, deg
β, deg
Anal. Calcd for C39H33ClOP2Pd: C, 64.92; H, 4.61.
Found: C, 65.59; H, 5.18. 1H NMR (400 MHz, CDCl3):
δ 7.66–6.93 (m, ArH, 28H), 5.89 (m, CH, 1H), 5.38 (m,
CH2, 2H), 3.37 (m, CH2, 2H). 31P{1H} NMR (162 MHz,
γ , deg
V , Å3
Z
ρcalc, gm−3
μ (MoKα), mm−1
F(000)
1.498
0.953
756
2
2
CDCl3): δ 156.2 (d, JPP = 29 Hz), 17.4 (d, JPP
=
2
2
29 Hz) and 146.6 (d, JPP = 439 Hz), 30.8 (d, JPP
439 Hz). MS (EI): m/z = 685.1 (M-Cl).
=
crystal size, mm
T (K)
0.23 × 0.17 × 0.14
150(2)
2θ range, (◦)
total no. reflns
no.of indep reflns
GOF (F2)
R1a
3.30–25.00
12084
5799 [Rint 0.0220]
2.10 Synthesis of [Ph2P{OC6H3(C3H5)-o}Pd(η2-dppm)]
OTf (10)
1.128
0.0367
0.1091
A solution of [{PPh2(OAr)}PdCl]2(8)(0.042 g,
0.045 mmol) in tetrahydrofuran (10 mL) was added
wRb2
drop-wise to a solution of bis(diphenylphosphino) aR=ꢀꢁFo|−|Fcꢁ/ꢀ|Fo|,bRw={[ꢀw(Fo2 −Fc2)/ꢀ w(F2o)2]} ,
1/2
w=1/[σ2(F2o) + (xP)2], where P=(Fo2 + 2F2c)/3
methane (dppm) (0.035 g, 0.091 mmol) and AgOTf

776
Singappagudem Govindaraju et al.
using CRYSALISPRO RED software. The structure
was solved by direct methods using SHELXS-97 and
refined by full matrix least squares with SHELXL-
97,10 refining on F2. The positions of all the atoms
were obtained by direct methods. All non-hydrogen
atoms were refined anisotropically. The hydrogen
atoms were placed in geometrically constrained posi-
tions and refined with isotropic temperature factors,
generally 1.2*U eq of their parent atoms. Crystallo-
graphic data and other experimental details are sum-
marized in table 1 and bond parameters are listed in
table 2.
Ph
P
OPPh2
O
O
1
2
The slow addition of dichloromethane solution of
[Ru(η6-p-cymene)Cl2]2 to 1 or 2 in 1:2 molar ratio
at room temperature afforded [Ru{PPh2(OAr)}(η6-p-
cymene)Cl2] (3) and [Ru{PPh(OAr)2}(η6-p-cymene)Cl2]
(4), respectively. The 31P NMR spectrum of 3 shows
a singlet at 113.6 ppm, whereas that of 4 appeared at
141.5 ppm. The 1H NMR spectra of both the complexes
are almost identical with the ligands, except peaks due
to the p-cymene moiety. Mass spectra of 3 and 4 show
peaks correspond to M-Cl ions at m/z 589.2 and 644.8,
respectively. The structure of 3 was confirmed by a
single crystal X-ray diffraction study.
Table 2. Selected bond distances (Å) and bond angles (◦) for 3.
Bond distances (Å)
Bond angles (◦)
Ru1–Cl1
Ru1–Cl2
Ru1–P1
P1–C26
P1–O1
2.4126(8)
Cl1–Ru1–Cl2
Cl1–Ru1–P1
Cl2–Ru1–P1
O1–P1–C26
87.58(3)
88.16(3)
91.14(3)
2.4112(8)
2.3120(8)
1.818(3)
1.627(2)
103.68(14)
Ph
Ru
Cl
Ph
P
P 2
O
Cl
Ru
Cl
Cl
O
O
3. Results and discussion
The reaction of chlorodiphenylp◦hosphine with 2-
allylphenol in 1:1 molar ratio at 0 C, in the presence
of triethylamine leads to the formation of Ph2P(OAr)
[Ar = C6H4(o-C3H5)] (1). A similar reaction of
dichlorophenylphosphine with 2-allylphenol in 1:2
molar ratio gave PhP(OAr)2 (2), in good yield. The
compounds 1 and 2 are air and moisture sensitive vis-
cous liquids. The 31P NMR spectra of 1 and 2 con-
sist of single resonances at 107.8 ppm and 158.4 ppm,
3
4
The treatment of AuCl(SMe2) with 1 or 2 in dichloro-
methane at room temperature resulted in the formation
of [Au{PPh2(OAr)}Cl] (5) and [Au{PPh(OAr)2}Cl]
(6). The 31P NMR spectra of complexes 5 and 6 con-
sist of single resonances, respectively, at 111.2 ppm and
135.1 ppm. The reaction between Pd(COD)Cl2 and 2
affords Pd{PPh(OAr)2}2Cl2 (7). The 31P NMR spec-
trum of compound 7 shows a sharp singlet at 118.8 ppm.
The 1H NMR and elemental analyses data are in accor-
dance with the proposed structures.
1
respectively. H NMR spectra of 1 and 2 show mul-
tiplets around 3.4 and 6.9 ppm for allylic CH2 and
CH protons, respectively. Mass spectrum of 1 shows
a molecular ion peak at 319.2 corresponding to M+1
ion.
Cl
Au
Cl
Au
Ph
P
Ph
P
O
O
O
OPPh2
P
O
O
O
Pd
Ph
Cl
Cl
5
6
7

Phosphinite and phosphonite ligands
777
Ph2
P
Pd
Ph2
P
Pd
Ph2
P
Cl
Cl
Cl
Cl
8a
Ph2P
O
O
O
O
Pd
Pd
Pd(COD)Cl2,
O
P
Ph2
Δ
toluene,
8b
1
dppm, THF, 4 h
AgOTf
PPh3 toluene, 4 h
Ph2
P
Ph2
Ph2
OTf
Ph2
O
O
P
Cl
O
P
P
PPh3
Pd
Pd
Pd
P
PPh3
Ph2
Cl
9b
9a
10
Scheme 1. Orthopalladation reaction of ligand 1.
with a 2 JPP of 29.2 Hz, whereas trans complex, 9b con-
sists of two doublets centered at 146.6 and 30.8 ppm
with a 2 JPP of 438.9 Hz. In mass spectrum, the mixture
of 9a and 9b show a peak at m/z 685.1 for M-Cl ion.
To further confirm the orthometallation reac-
tion, the mixture of 8a and 8b was treated with
bis(diphenylphosphino)methane (dppm) in the presence
of silver triflate in tetrahydrofuran at room temperature
to yield a cationic complex, [Ph2P{OC6H3(C3H5)-o}
Pd(η2-dppm)]OTf (10). The 31P NMR spectrum (see
figure 1) of 10 consists of three doublet of doublets
centered at 149.7 ppm, −20.8 ppm and −25.7 ppm, thus
confirming the presence of three different phosphorus
The reaction of Pd(COD)Cl2 with Ph2P(OAr) (1) in
toluene under reflux conditions yielded a mixture of cis
and trans isomers [Pd(PPh2(OAr))Cl]2 (8a and 8b), in
1:1 ratio as confirmed by 31P NMR spectrum, which
show two singlets at 151.9 and 151.1 ppm, probably
for cis and trans isomers, respectively (scheme 1).5
Evidence for orthometallation came from the elemental
analysis, mass spectrometry and from further reactions.
The cis and trans mixture (8a and 8b) on treatment
with one equivalent of triphenylphosphine in toluene
at room temperature also afforded a mixture cis- and
trans-[Ph2(OAr)PPd(PPh3)Cl] (9a and 9b), in 1:1 ratio,
as indicated by its 31P NMR spectrum. The presence
of cis and trans isomers was unambiguously confirmed
from its 31P NMR spectrum due to the large difference
in 2 JPP values. The 31P NMR spectrum of cis compound,
9a shows two doublets centered at 156.2 and 17.4 ppm
2
centers. A doublet of doublets at 149.7 with JPP of
385.3 and 17.8 Hz was assigned to coordinated phos-
phorus of phosphinite ligand. The upfield resonances at
−25.7 and −20.8 were assigned to phosphorus centers
Figure 1. 31P NMR spectrum of [Ph2P{OC6H3(C3H5)-o}Pd(η2-dppm)]OTf (10).

778
Singappagudem Govindaraju et al.
ruthenium(II) complexes were synthesized in good
yield. The structure of ruthenium(II) complex (3) was
determined by single crystal X-ray diffraction study
which depicts ruthenium centre adopting typical piano-
stool geometry. Ligand 1 undergoes orthometallation on
treatment with Pd(COD)Cl2 under reflux conditions.
Supplementary information
CCDC-870096 (3) contains the supplementary crystal-
lographic data for this paper. This can be obtained free
of charge from the Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif.
Acknowledgements
We thank the Department of Science and Technology
(DST), New Delhi, for financial support for this work.
GSA thanks the Council of Scientific and Industrial
Research (CSIR), New Delhi, for research fellowships
(JRF & SRF). We also thank the Department of Chem-
istry and National Single Crystal X-ray Diffraction
Facility, Indian Institute of Technology (IIT) Bombay,
for spectral, analytical data and X-ray structure deter-
mination.
Figure 2. Crystal structure of complex 3 with atom num-
bering scheme. Thermal ellipsoids are drawn at the 50%
probability level and all hydrogen atoms are omitted for
clarity.
of dppm, cis and trans to phosphinite ligand, respec-
tively. Mass spectrum of 10 shows a peak at m/z 806.7
for M-OTf ion.
References
3.1 X-ray structure analysis of
1. Agbossou F, Carpentier J F, Hapiot F, Suisse I
and Mortreux A 1998 Coord. Chem. Rev. 178–180
1615
[Ru{Ph2P(OAr)}(η6-p-cym)Cl2] (3)
The crystals for single crystal X-ray diffraction study
were obtained by the slow evaporation of chloroform–
petroleum ether solution of 3 at room temperature. The
crystallographic data are reported in table 1, and the
molecular structure of the complex 3 is shown in fig-
ure 2 while selected bond lengths and angles are listed
in table 1. The asymmetric unit contains one molecule
of 3 and a CHCl3 molecule as solvent of crystalliza-
tion. The ruthenium center consists of a p-cymene
group, coordinated in η6-fashion to form a three-legged
‘piano-stool’ structure, along with one phosphorus and
two chloride ions. The Cl1–Ru–P1 and Cl2–Ru–P1
bond angles are 88.16◦ and 91.14◦, respectively. The
Cl1–Ru–Cl2 bond angle is (87.58◦) comparable with
the same observed in analogues ruthenium complexes
containing tertiary phosphines.11
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