Mononuclear and heterodinuclear transition metal complexes of functionalized phosphines. Crystal and molecular structures of (see abstract)

Article abstract of DOI:10.1016/j.jorganchem.2004.07.041

Transition metal complexes of phosphine ethers (Ph₂ H₄OCH₂OCH₃-o and PhP(C₆ H₄OCH₂OCH₃-o) ₂) and phosphinophenol, Ph₂H₄OH-o are descri

Full text of DOI:10.1016/j.jorganchem.2004.07.041

Journal of Organometallic Chemistry 689 (2004) 3335–3349
www.elsevier.com/locate/jorganchem
Mononuclear and heterodinuclear transition metal complexes of
functionalized phosphines. Crystal and molecular structures of
[Mo(CO)5(RPC6H4OCH2OCH3-o)](R = Ph, C6H4OCH2OCH3-o),
[Ru(Ph2PC6H4O-o)3], [Pd(Ph2PC6H4O-o)2] and
[PdCl(Ph2PC6H4O-o)(Ph2PC6H4OH-o)]
a
a,
b
Srinivasan Priya , Maravanji S. Balakrishna *, Joel T. Mague
a
Department of Chemistry, Indian Institute of Technology, Bombay, Mumbai 400 076, India
b
Department of Chemistry, Tulane University, New Orleans, Louisiana, LA 70118, USA
Received 22 June 2004; accepted 24 July 2004
Available online 28 August 2004
Abstract
Transition metal complexes of phosphine ethers (Ph2PC6H4OCH2OCH3-o and PhP(C6H4OCH2OCH3-o)2) and phosphinophe-
nol, Ph2PC6H4OH-o are described. Phosphine ethers react with Group 6 metal carbonyls to form complexes of the type
[M(CO)4L2] and [M(CO)5L] (M = Mo, Cr, W). The reaction of Ph2PC6H4OCH2OCH3-o with RuCl3 Æ 3H2O gave ruthenium(III)
complex, [Ru(Ph2PC6H4O-o)3] through the elimination of CH3OCH2Cl whereas the reaction with CpRu(PPh3)2Cl resulted in the
formation of [CpRu(Ph2PC6H4O-o)PPh3]. Treatment of Ph2PC6H4OCH2OCH3-o with rhodium(I) derivatives resulted in the forma-
tion of complexes with the phosphine exhibiting both mono- and bidentate modes of coordination involving the phosphorus center
and the phenolic oxygen. The reaction of Ph2PC6H4OCH2OCH3-o with [PdCl2(COD)] led to the isolation of two mononuclear com-
plexes, [PdCl(Ph2PC6H4O-o)(Ph2PC6H4OH-o)] cocrystallized with phosphonium salt, [Ph2P(CH2OCH3)C6H4OH-o]Cl and
[Pd(Ph2PC6H4O-o)2] as confirmed by X-ray diffraction studies. The former shows extensive hydrogen bonding interactions between
the complex and the phosphonium salt. The metalloligand, Cp2Zr(OC6H4PPh2-o)2 obtained by the reaction of Cp2ZrCl2 with
Ph2PC6H4OH-o form heterobimetallic complexes with Mo(0), Re(I) and Ni(0) carbonyl derivatives. The reactions of
Cp2Zr(OC6H4PPh2-o)2 with metal halides such as M(COD)Cl2(M = Pd, Pt) and CpRuCl(PPh3)2 afforded metallacycles,
[M(Ph2PC6H4O-o)2] and [CpRu(PPh2C6H4OH-o)(PPh2C6H4O-o)], respectively via transmetallation.
ꢀ 2004 Elsevier B.V. All rights reserved.
Keywords: Functionalized phosphines; Phosphinoethers; Complexes; Metallacycles; Crystal structure
1. Introduction
to a low valent metal center and stabilize it in a lower oxi-
dation state and enhance the chelating possibilities
throughtheetherO-center, (b)ThelabileM–Ocoordinate
bond in the chelate complex can be readily cleaved when it
isrequiredduringthecatalyticandbiologicalprocesses.In
contrast, the functional groups caneffectively bind tomet-
als in their high-valent states to give metallo-ligands with
dangling phosphorus(III) centers. These phosphorus cen-
ters can bind to low-valent metals to give heterobimetallic
complexes without a formal metal–metal bond yet with
Phosphines with pendant ether functionalities are of
considerable interest, in particular with respect to the
development of potential catalysts [1–3] due to the follow-
ing advantages:(a) Phosphorus(III) atomscancoordinate
*
Corresponding author. Tel.: +91 22 2576 7181; fax: +91 22 2576
7152/2572 3480.
E-mail address: krishna@iitb.ac.in (M.S. Balakrishna).
0022-328X/$ - see front matter ꢀ 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2004.07.041

3336
S. Priya et al. / Journal of Organometallic Chemistry 689 (2004) 3335–3349
two disparate metals in close proximity. Such heterobime-
tallic complexes could be very effective in activating small
organic molecules due to the ‘‘cooperative effect’’ that
arises as a consequence of electron sink and reservoir nat-
ure of high-valent and the low-valent metals, respectively
[4]. As part of our interest [5] and of others [3,6] in phos-
phines with various functionalities, herein we report the
transition metal complexes of phosphine ethers,
Ph2PC6H4OCH2OCH3-o (1), PhP(C6H4OCH2OCH3-o)2
(2) and phosphino phenol, Ph2PC6H4OH-o.
Perspective views of complexes 8 and 9 are shown in
Fig. 1 while crystallographic data, selected bond dis-
tances and bond angles are given in Tables 1 and 2.
The crystal structure of 9 reveals the presence of two
independent molecules in the asymmetric unit, which
differ somewhat in the bond distances and bond angles
involving the metal center. The structures of 8 and 9
show octahedral environment around molybdenum cen-
ters with trans angles in the range of 174.7–175.5ꢁ (for
complex 8) and 171.0–175.1ꢁ (for complex 9). The cis
angles vary in the range of 85.7–93.0ꢁ (for complex 8)
and 83.7–97.3ꢁ (for complex 9). The Mo–P bond dis-
2. Results and discussion
˚
tances in 8 and 9 are 2.570(1) A and 2.572(2), 2.578(2)
˚
A, respectively. The Mo–C bond trans to the Mo–P
˚
bond (av. 1.985 A) is slightly shorter than the other
2.1. Phosphine-ethers
˚
Mo–C bond distances (av. 2.044 A) in both the com-
plexes 8 and 9 as expected.
The hemilabile phosphine ethers, Ph2PC6H4O-
CH2OCH3-o (1) and PhP(C6H4OCH2OCH3-o)2 (2) were
synthesized from methoxymethylphenyl ether and
Ph2PCl/PhPCl2 following the literature [7] procedures.
When [M(CO)4L2] (L2 = (piperidine)2, NBD or COD)
was treated with ligands 1 and 2, tetracarbonyl com-
plexes of the type, [M(CO)4L2] (3–7) (M = Cr, Mo or
W, L = 1 or 2) were obtained in good yield. The IR spec-
tra of the chromium complexes 3 and 4 show single band
in the carbonyl region indicating the formation of trans-
isomers. The molybdenum and tungsten complexes 5–7
each show four strong absorptions in the carbonyl re-
gion and so are cis-isomers. The 31P NMR chemical
shifts (see Section 4) of disubsituted tetracarbonyl com-
plexes, 3–7 are more shielded as moved from chromium
to tungsten down the group. Reactions of 1 and 2 with
Mo(CO)6 in equimolar ratio, afforded monosubstituted
complexes, [Mo(CO)5(PPh2C6H4OCH2OCH3-o)] (8)
and [Mo(CO)5{PPh(C6H4OCH2OCH3-o)2}] (9), respec-
tively. The 31P NMR spectra of 8 and 9 show single
resonances at 29.5 and 22.6 ppm with the coordination
shifts of 45.5 and 49.0 ppm, respectively. The 1H
NMR spectrum of complex 8, shows a single resonance
due to the methylene protons whereas the same in com-
plex 9 appears as an AB quartet indicating their non-
equivalence. The IR spectra of 8 and 9 show three
bands in the carbonyl region as expected. The structures
of complexes 8 and 9 have been established by single
crystal X-ray diffraction studies.
When ligand 1 was treated with RuCl3 Æ 3H2O un-
der reflux conditions, a neutral ruthenium(III) metall-
acycle, [Ru(Ph2PC6H4O-o)3] (10) was obtained in good
yield. The ether linkage is cleaved during complexa-
tion leading to the formation of the phenolate ion,
presumably with the elimination of methoxymethyl
chloride. The phenolate oxygens bind to the ruthe-
nium center forming three five-membered metallacy-
cles. In contrast, phosphine-ether ligands of the type
R2PCH2CH2OMe-o, Ph2PC6H4OMe-o when reacted
with RuCl3Æ3H2O, form exclusively bischelate com-
plexes, trans-[RuCl2 (R2PCH2CH2OMe-o)2] and
[RuCl2(Ph2PC6H4OMe-o)2], respectively [2]. Thus, the
cleavage could be presumably due to the presence of
additional OCH3 group and which facilitates the elim-
ination of methoxymethyl chloride (caution: Methoxy-
methyl chloride is highly toxic and the reaction has to
be performed in a very efficient fume hood). The 31P
NMR spectrum of 10 shows a broad peak around
49 ppm owing to its paramagnetic nature. However,
structure of complex 10 was confirmed by single crys-
tal X-ray diffraction study. The perspective view of
molecule 10 is shown in Fig. 2. The crystallographic
data, selected bond distances and bond angles are
listed in Tables 1 and 3, respectively. The core
RuO3P3 has the three phosphorus and three oxygen
centers disposed in a meridional arrangement, conse-
quently pairs of donors are mutually trans to each
other, O(1)/O(2) and P(2)/P(3), whereas P(1) is trans
to O(3). The Ru–P(1) and Ru–P(2) bond distances
˚
are the same (2.347(1) A) whereas the Ru–P(3) bond
which is trans to Ru–P(2) is longer with a bond dis-
O
O
CO
M
˚
tance of 2.374 A. Similarly, the bond distances of
RPhP
OC
PPhR
PPhR
OC
OC
O
CO
CO
O
˚
Cr
Ru–O(1)‚Ru–O(3) = 2.043(2) A are longer than the
OC
RPhP
O
O
CO
˚
Ru–O(2) (2.006(2) A) bond distance which is trans
to Ru–O(1) bond.
O
The reaction of 1 with CpRuCl(PPh3)2 in equimolar
ratio gave CpRu(PPh3)(PPh2C6H4O-o) (11) in 42%
yield. The ether linkage is cleaved during complexation
O
5 M = Mo, R = Ph
6 M = W, R = Ph
7 M = W, R = C6H4OCH2OCH3
3 R = Ph
4 R = C6H4OCH2OCH3

S. Priya et al. / Journal of Organometallic Chemistry 689 (2004) 3335–3349
3337
Fig. 1. ORTEP plot of [Mo(CO)5(PPh2C6H4OCH2OCH3-o)] (8) and [Mo(CO)5{PPh(C6H4OCH2OCH3-o)2}] (9) with thermal ellipsoids are drawn at
50% probability level. Hydrogen atoms are omitted for clarity.
Table 1
Crystallographic data for complexes 8, 9, 10, 16 and 17
Complex 8
25H19MoO7P
558.31
Complex 9
Complex 10
Complexes 16 and 18
Complex 17
Empirical formula
Formula weight
C
C27H23MoO9P
618.36
Triclinic
C54H42O3P3Ru Æ CH2Cl2
1017.78
Monoclinic
P21/c (No. 14)
18.468(3)
13.295(2)
18.867(3)
90
C36H29ClO2P2Pd Æ C20H20O2PCl
1056.18
C37.5H31O2P2PdCl3
788.31
Triclinic
Crystal system
Space group
Monoclinic
P21/n (No. 14)
14.9920(9)
11.3395(5)
15.6674(8)
90
Triclinic
ꢀ
ꢀ
ꢀ
P1 (No. 2)
P1 (No. 2)
P1 (No. 2)
a
b
c
9.0561(3)
16.6920(8)
19.1080(9)
99.074(4)
103.669(4)
86.875(4)
2771.2(2)
4
11.2638(6)
13.4451(7)
17.713(1)
89.822(1)
78.018(1)
71.691(1)
2485.6(2)
2
11.372(2)
11.829(2)
14.393(3)
89.891(3)
73.388(3)
89.717(4)
1855.3(6)
1
a
b
c
108.093(6)
90
91.394(2)
90
V
2531.8(2)
4
1.465
4631.1(3)
4
1.460
Z
D(calc.)
k (Mo Ka)a
1.482
1.411
1.411
˚
A
0.71073
0.6
293
0.71073
0.6
293
0.71073
0.6
100
0.71073
0.6
100
0.71073
0.8
100
l (Mo Ka) (mm)
Temperature (K)
h min–max (ꢁ)
1.6–25.1
0.0276
0.0812
1.5–25.1
0.0470
0.1359
1.1–28.3
0.0590
0.1404
1.6–28.3
0.0432
0.0994
1.5–23.3
0.0723
0.2108
Rb
wRc
a, b
0.03676, 0.6313
0.0163, 0.9343
0.0566, 10.3774
0.0480, –
0.1185, –
2
w ¼ 1=½r2ðF 2oÞ þ ðaPÞ þ bPꢁ; P ¼ 1=3½F o2 þ 2F 2c ꢁ.
a
Graphite monochromated.
R = jFo ꢀ Fcj/ jFoj.
P
P
b
h
.
i
1=2
P
P
2
c
Rw
¼
wðF 2o ꢀ F 2c Þ
wðF 2oÞ
.
leading to the formation of the phenolate ion, presuma-
bly with the elimination of methoxymethyl chloride. The
phenolate oxygen binds to the ruthenium center forming
The reaction of 1 with [Rh(CO)2Cl]2 resulted in the
formation of a neutral chelate complex, [Rh(CO)Cl-
(PPh2C6H4OCH2OCH3-o)] (12) in good yield. The IR
1
a
five-membered metallacycle. In
a
similar way,
spectrum of 12 shows mCO at 1956 cmꢀ1 and the H
Ph2PC6H3(2,6-OCH3)2 reacted with [(g6-p-cymene)
RuCl2]2 to give [(g6-p-cymene)RuCl{PPh(2,6-MeO)2-
C6H3(2-O-6-MeOC6H3)}] presumably through the elim-
ination of one of the methyl group as CH3Cl to form a
five-membered metallacycle [8]. The same compound is
also obtained directly from Ph2PC6H4OH-o. 31P NMR
spectrum of 11 exhibits two doublets at 57.5 and 44.2
ppm with a 2JPRuP coupling of 35.1 Hz. Further support
for the formation of 11 comes from its mass spectral
data and micro analytical data.
NMR spectrum shows shift in the resonances for the
CH2 and CH3 protons as compared to the free ligand
implying the binding of the oxygen to the metal center.
The 31P NMR spectrum of 12 shows a doublet at 59.5
1
ppm with a JPRh coupling of 173.8 Hz.
The reaction of 1 with [Rh(COD)Cl]2 gave a mixture
of two complexes, [Rh(COD)(PPh2C6H4OCH2OCH3-
o)Cl] (13) and [Rh(COD)(l-PPh2C6H4OCH2OCH3-
o)]2Cl2 (14) in 3:1 ratio as indicated by the 31P NMR
spectroscopic data. The 31P NMR spectrum of the

3338
S. Priya et al. / Journal of Organometallic Chemistry 689 (2004) 3335–3349
Table 2
mixture. Two sets of chemical shifts were observed for
the CH2 and CH3 protons in a 3:1 ratio with one set
of chemical shifts essentially in the same position that
of ligand (due to complex 13) whereas the other set
shows chemical shifts with considerable shielding (due
to complex 14) indicating the coordination of the phe-
nolic oxygen to the metal center. However, after crystal-
lization, complex 13 is obtained exclusively and attempts
to isolate the cationic complex 14 have been unsuccess-
ful. The cationic complex, [Rh(COD)(PPh2C6H4O-
CH2OCH3-o)]BF4 (15) was obtained in a separate
reaction of 1 with [Rh(COD)Cl]2 in presence of AgBF4.
The 31P NMR spectrum of 15 exhibits a doublet at 34.0
˚
Selected bond distances (A) and bond angles (ꢁ) for compounds 8 and
9
Compound 8
Compound 9
˚
Bond distances (A)
Mo–P
2.570(1)
2.059(3)
2.049(3)
1.990(3)
1.842(3)
1.134(4)
1.124(4)
2.033(3)
2.031(3)
1.837(3)
1.836(3)
1.130(4)
1.141(4)
1.142(4)
Mo(1)–P(1)
Mo(1)–C(2)
Mo(1)–C(4)
P(1)–C(6)
2.575(2)
2.032(7)
2.044(7)
2.568(2)
2.016(9)
2.568(2)
1.844(7)
2.039(7)
2.052(7)
1.989(7)
2.042(7)
1.848(7)
1.838(7)
Mo–C(2)
Mo–C(3)
Mo–C(5)
P–C(12)
P(1)–C(18)
Mo(2)–P(2)
P(2)–C(33)
Mo(1)–C(1)
Mo(1)–C(3)
Mo(1)–C(5)
P(1)–C(12)
P(2)–C(39)
P(2)–C(45)
O(1)–C(1)
O(3)–C(3)
Mo–C(1)
Mo–C(4)
P–C(6)
1
ppm with a JRhP coupling of 159.2 Hz. The coordina-
tion chemical shift is 60.4 ppm (see Scheme 1).
P–C(18)
O(2)–C(2)
O(4)–C(4)
O(5)–C(5)
The reaction of 1 with [Pd(COD)Cl2] in 2:1 molar ra-
tio leads to the formation of a mixture of products as
evident from the 31P NMR spectroscopic data. Frac-
tional crystallization of the crude product using a
CH2Cl2–diethylether mixture (see Section 4) led to the
isolation of three different products 16–18 which are
characterized by micro analytical data, mass, IR, and
NMR spectroscopic data. Formation of complexes,
[PdCl(PPh2C6H4O-o) (PPh2C6H4OH-o)] (16) and [Pd
(PPh2C6H4O-o)2] (17) involves the cleavage of a C–O
(ether linkage) bond of the ligand, which forms the phe-
nolate ion, presumably with the elimination of methoxy-
methylchloride as observed in the case of ruthenium
complexes 10 and 11. Similar reaction of Pd(COD)Cl2
with analogous ligand, PPh2C6H4OCH3 affords the sim-
ple chelate complex, PdCl2(PPh2C6H4OCH3-o)2 [2,9]. In
complex 16, one of the ligands forms a five-membered
metallacycle whereas the other binds only through the
phosphorus center and the phenolic oxygen is proto-
nated. Complex 17 is consists of two five-membered
metallacycles (Scheme 2). Along with these two
complexes, the phosphonium salt, [Ph2P(CH2OCH3)-
C6H4OH-o]Cl (18) is also formed, which is co-crystal-
lized with 16. The formation of 18 may be attributed
to the quaternization of the phosphorus(III) center in
1 by CH3OCH2Cl which was eliminated during com-
plexation. Such phosphonium salt formation was not
observed in the deprotection reactions of ligands 1 and
2 with anhydrous HCl. The 31P NMR spectrum of 16
Bond angles (ꢁ)
P–Mo–C(1)
P–Mo–C(3)
92.0(1)
91.2(1)
174.7(1)
118.5(1)
100.7(1)
102.5(1)
86.7(1)
97.7(1)
91.3(1)
115.2(1)
114.5(1)
103.2(1)
P(1)–Mo(1)–C(1)
P(1)–Mo(1)–C(3)
P(1)–Mo(1)–C(5)
Mo(1)–P(1)–C(6)
Mo(1)–P(1)–C(18)
P(1)–Mo(1)–C(2)
P(1)–Mo(1)–C(4)
Mo(1)–P(1)–C(12)
C(6)–P(1)–C(12)
C(12)–P(1)–C(18)
97.3(2)
89.2(2)
P–Mo–C(5)
175.1(2)
119.6(2)
116.0(2)
90.5(2)
Mo–P–C(12)
C(6)–P–C(12)
C(12)–P–C(18)
P–Mo–C(2)
88.3(2)
P–Mo–C(4)
C(1)–Mo–C(2)
Mo–P–C(6)
112.1(2)
105.3(3)
101.4(3)
Mo–P–C(18)
C(6)–P–C(18)
2
shows two doublets at 47.2 and 20.8 ppm with a JPP
coupling of 12.3 Hz indicating that one of the ligand
binds to the metal in a monodentate fashion whereas
the other forms a metallacycle. The 31P chemical shift
due to the phosphonium salt, [Ph2P(CH2OCH3)-
C6H4OH-o]Cl (18) appears as a singlet at 16.1 ppm.
Complex 17 shows a single resonance at 43.7 ppm in
its 31P NMR spectrum indicating the equivalent nature
of both the phosphorus centers.
Fig. 2. ORTEP plot of [Ru(Ph2PC6H4O-o)3] (10). Ellipsoids are drawn
at the 50% probability level. Hydrogen atoms are omitted for clarity.
reaction mixture shows two doublets at 23.0 and 48.4
1
ppm, respectively for 13 and 14 with JPRh couplings
1
of 149.6 and 141.9 Hz. The H NMR spectrum also
reveals the presence of two complexes in the reaction
The structure of complex 16 co-crystallized with 18
was established by single crystal X-ray diffraction stud-
ies. The structures are shown in Fig. 3 and crystallo-

S. Priya et al. / Journal of Organometallic Chemistry 689 (2004) 3335–3349
3339
Table 3
˚
Selected bond lengths (A) and bond angles (ꢁ) for 10
˚
Bond distances (A)
Ru(1)–P(1)
Ru(1)–P(3)
Ru(1)–O(2)
P(1)–C(1)
2.347(1)
Ru(1)–P(2)
Ru(1)–O(1)
Ru(1)–O(3)
P(2)–C(19)
2.347(1)
2.043(2)
2.043(2)
1.809(4)
2.374(1)
2.006(2)
1.799(3)
1.813(4)
P(3)–C(37)
Bond angles (ꢁ)
P(1)–Ru(1)–P(2)
P(1)–Ru(1)–O(1)
P(1)–Ru(1)–O(3)
P(2)–Ru(1)–O(1)
P(2)–Ru(1)–O(3)
P(3)–Ru(1)–O(2)
O(1)–Ru(1)–O(2)
O(2)–Ru(1)–O(3)
97.47(3)
81.1(1)
172.1(1)
95.0(1)
84.9(1)
95.2(1)
174.2(1)
94.3(1)
P(1)–Ru(1)–P(3)
P(1)–Ru(1)–O(2)
P(2)–Ru(1)–P(3)
P(2)–Ru(1)–O(2)
P(3)–Ru(1)–O(1)
P(3)–Ru(1)–O(3)
O(1)–Ru(1)–O(3)
95.39(3)
93.5(1)
167.13(3)
83.6(1)
87.5(1)
82.5(1)
91.2(1)
2+
(Cl)2
O
O
PPh2
P
Ph2
O
O
Rh
Rh
Rh
+
O
P
Cl
Ph2
13
14
O
[Rh(COD)Cl]2
Ph2
P
Ph2
P
PPh2
[Rh(COD)Cl]2
AgBF4
OC
Cl
[Rh(CO)2Cl]2
Rh
Rh
BF4
O
O
O
O
O
O
15
1
12
Scheme 1.
graphic data, selected bond distances and bond angles
are given in Tables 1 and 4.
lattice structure is shown in Fig. 4, where the com-
plex 16 and the phosphonium ion 18 are placed alter-
nately and are linked by Clꢀ ions. The different
hydrogen bonding parameters are summarized in
Table 5.
The structure of bischelate complex 17 was also
established by single crystal X-ray diffraction studies.
The perspective view of molecule 17 is shown in Fig. 5
and crystallographic data, selected bond distances and
bond angles are given in Tables 1 and 6. In complex
17, palladium is in a distorted square planar environ-
ment with two phosphorus centers in mutually cis dispo-
sitions. The trans angles are: P(1)–Pd–O(2) = 173.1(2)
and P(2)–Pd–O(1) = 172.9(2)ꢁ and the cis angles varies
from 85.0(2)ꢁ to 101.8(1)ꢁ.
In complex 16, palladium is in a distorted square
planar environment with two phosphorus centers in
mutually cis dispositions. One of the ligands binds
in monodentate fashion keeping the OH group intact,
whereas the other ligand forms a five-membered met-
allacycle. The cis and trans angles are: 100.51(3)ꢁ
[P(1)–Pd–P(2)], 89.3(2)ꢁ [O(1)–Pd–Cl(1)] 173.49(3)ꢁ
and [Cl(1)–Pd–P(1)], 174.18(6)ꢁ [P(2)–Pd–O(1)],
respectively. The Pd–P(1) and Pd–P(2) bond distances
˚
are 2.241(1) and 2.251(1) A, respectively. The P(1)–
Pd–O(1) angle of 84.88(6)ꢁ is also comparable with
the same in analogous five-membered metallacycles
[10]. The chloride ion in the phosphonium salt is held
by five intermolecular hydrogen bonding interactions
of which two are the O–H. . .Cl type and the remain-
ing three are of the C–H. . .Cl type. This molecule
also exhibits one intramolecular and one intermolecu-
lar C–H. . .O type hydrogen bonding interaction. The
The reaction of 1 with [Pd(COD)Cl2] in the presence
of two moles of AgBF4 resulted in the formation of ionic
complex, [Pd(PPh2C6H4OCH2OCH3-o)2](BF4)2 (19) as
shown in Scheme 2. The 31P NMR spectrum of 19 shows
a single resonance at 45.4 ppm.

3340
S. Priya et al. / Journal of Organometallic Chemistry 689 (2004) 3335–3349
PPh2
O
[Pd(COD)Cl2]
Cl
OH
Ph2
P
Ph2
P
HO
+
+
Pd
O
Ph2P
Cl
1
O
O
[Pd(COD)Cl2]
AgBF4
16
18
+
Ph2
P
Ph2
Ph2
P
Ph2
P
P
BF
2
4
Pd
Pd
O
O
O
O
O
17
O
19
Scheme 2.
Fig. 3. ORTEP plot of [PdCl(PPh2C6H4O)(PPh2C6H4OH-o)] (16) co-crystallized with [Ph2P(CH2OCH3)C6H4OH-o]Cl (18). Ellipsoids are drawn at
the 50% probability level. Hydrogen atoms are omitted for clarity.
Table 4
NMR spectroscopic data. The reactions of ligands 1
and 2 with [Pt(COD)I2] in 2:1 molar ratio gave cis-
˚
Selected bond distances (A) and bond angles (ꢁ) for 16 and 18
˚
Bond distances (A)
[Pt(PPh2C6H4OCH2OCH3-o)2I2] (21) and cis-[Pt{PPh-
(C6H4OCH2OCH3-o)2}2I2] (22), respectively in good
yields. The 31P NMR spectra of 21 and 22 show single
Pd–Cl(1)
Pd–P(2)
2.360(1)
2.251(2)
1.817(3)
1.773(4)
Pd–P(1)
Pd–O(1)
2.241(1)
2.059(2)
1.781(3)
1.790(3)
P(23)–C(55)
P(3)–C(43)
P(3)–C(37)
P(3)–C(49)
1
resonances at 5.6 and 1.7 ppm with JPtP coupling of
1
2565 and 2611 Hz, respectively. The H NMR spectral
data supports the monodentate nature of the ligand
Bond angles (ꢁ)
Cl(1)–Pd–P(1)
1
whereas the large JPtP coupling supports the cis geom-
173.50(3)
89.3(2)
84.9(2)
Cl(1)–Pd–P(2)
P(1)–Pd–P(2)
O(1)–Pd–P(2)
85.40(3)
100.51(3)
174.2(1)
111.1(1)
106.1(1)
108.5(2)
Cl(1)–Pd–O(1)
O(1)–Pd–P(1)
etry around the metal center.
1
The H and 31P NMR spectral data for compounds
3–22 are given in Table 7.
C(37)–P(3)–C(55)
C(37)–P(3)–C(49)
C(43)–P(3)–C(49)
107.2(2)
114.4(1)
109.4 (2)
C(37)–P(3)–C(43)
C(49)–P(3)–C(55)
C(43)–P(3)–C(55)
2.2. Phosphinophenol
The reaction of 1 with anhydrous HCl regenerates
hydroxy functionality to give phosphinophenol,
Ph2PC6H4OH-o [7].
The reaction of Ph2PC6H4OH-o with Cp2ZrCl2 in the
presence of imidazole in dichloromethane gives the
metalloligand, Cp2Zr(OC6H4PPh2-o)2 (23) (Eq. 1).
The reaction of PhP(C6H4OCH2CH3-o)2 (2) with
[Pd(COD)Cl2] affords
[Pd{PPh(C6H4OCH2OCH3-
o)2}2Cl2] (20) in good yield (Scheme 3). The 31P NMR
spectrum of 20 shows a single resonance at 14.3 ppm.
The formation of 20 is further confirmed by its 1H

S. Priya et al. / Journal of Organometallic Chemistry 689 (2004) 3335–3349
3341
Fig. 4. (a) PLATON diagram of 16 and 18 showing O–H..Cl type intermolecular hydrogen bonding interactions. (b) The lattice structure showing
alternate arrangement of complex 16 and phosphonium salt 18 linked by hydrogen bonding.
Table 5
Different hydrogen bonding interactions present in 16 and 18
˚
dH..A (A)
˚
dD. . .A (A)
D–H. . .A
D–H–A (ꢁ)
O(2)–H(2). . .Cl(2)
O(3)–H(3). . .Cl(2)
C(21)–H(21)..Cl(2)
C(38)–H(38)..O(4)
C(40)–H(40). . .Cl(2)
C(45)–H(45). . .Cl(2)
C(50)–H(50). . .O(1)
2.1525
2.0887
2.8048
2.4293
2.7193
2.7371
2.3131
2.992(20)
2.915(2)
3.513(3)
3.117(4)
3.627(3)
3.592(4)
3.219(4)
178.99
167.99
132.11
128.03
160.07
150.11
159.29
Even though this compound was prepared by Miquel
et al. [11] in 1995 to date, only one heterobimetallic
complex, [Cp2Zr(OC6H4PPh2-o)2Rh(CO)Cl] is reported
[11].
Fig. 5. ORTEP plot of [Pd(PPh2C6H4O-o)2] (17). Ellipsoids are
drawn at the 50% probability level. Hydrogen atoms are omitted for
clarity.

3342
S. Priya et al. / Journal of Organometallic Chemistry 689 (2004) 3335–3349
Table 6
spectrum of 26 shows a single resonance at 34.3 ppm.
IR spectrum of 26 (mCO: 2004 vs and 1948 vs cmꢀ1
shows the shift of mCO towards higher wave number
when compared to the metal precursor, Ni(CO)2(PPh3)2
(mCO: 1999 s and 1943 vs cmꢀ1). Further evidence for the
structural composition of complexes 24–26 comes from
their mass spectral data.
˚
Selected bond distances (A) and bond angles (ꢁ) for 17
˚
Bond distances (A)
)
Pd–P(1)
Pd–P(2)
2.229(3)
2.224(3)
Pd–O(1)
Pd–O(2)
2.035(6)
2.035(6)
Bond angles (ꢁ)
P(1)–Pd–P(2)
P(1)–Pd–O(2)
P(2)–Pd–O(2)
101.8(1)
173.1(2)
85.0(2)
P(1)–Pd–O(1)
P(2)–Pd–O(1)
O(1)–Pd–O(2)
85.2(2)
172.9(2)
88.1(3)
The reactions of metalloligand, Cp2Zr(OC6H4PPh2-
o)2 with M(COD)Cl2 (M = Pd, Pt) in CH2Cl2 resulted
in the formation of chelate complexes [M(OC6H4PPh2-
o)2] (M = Pd, 17; Pt, 27), instead of the anticipated
heterobimetallics as shown in Scheme 5. The formation
of 17 and 27 could be due to the transmetallation of
metalloligand 23 through the elimination of Cp2ZrCl2.
OH
PPh2
PPh2
Imidazole,
O
O
1
The 31P and H NMR and mass spectral data supports
Cl
Cl
Zr
Zr
+
the formation of 17 and 27. The 31P NMR spectrum of
PPh2
CH2Cl2, r. t., 5 h.
1
27 shows a singlet at 19.0 ppm with JPtP coupling of
3540 Hz. The complexes 17 and 27 are reported in the
literature by the direct reaction of o-diphenylphosphino
phenol, Ph2PC6H4OH-o with corresponding metal
derivatives [7a,12].
23
ð1Þ
The reaction of metalloligand 23 with equimolar
quantity of Mo(CO)6 in benzene under reflux condition
afforded [(OC)4Mo(l-PPh2C6H4O-o)2ZrCp2] (24) as
shown in Scheme 4. The 31P NMR spectrum of product
shows a single resonance at 39.5 ppm indicating both the
phosphorus atoms are equivalent. The IR spectrum
shows four mCO bands indicating the presence of four
carbonyl groups on the molybdenum center with C2v
symmetry.
The reaction of fac-[Re(CO)3(CH3CN)2Br] with 23 in
equimolar ratio afforded [Br(OC)3Re(l-PPh2C6H4O-
o)2ZrCp2] (25) as shown in Scheme 4. The 31P NMR
spectrum of 25 shows doublet of doublets at 9.6 and
26.6 ppm with a 2JPReP coupling of 29.7 Hz, which indi-
cates that the arrangement of three CO ligands is merid-
ional. The 1H NMR spectrum of the compound 25
shows the peak corresponding to cyclopentadienyl pro-
tons at 6.37 ppm which are considerably deshielded as
compared to the same in metalloligand 23. IR spectrum
of 25 shows three bands in the carbonyl region support-
ing the meridional arrangement.
Upon the reaction of [CpRuCl(PPh3)2] with 23 in tol-
uene under reflux conditions, bright orange crystalline
product [CpRu(OC6H4PPh2-o)(PPh2C6H4OH-o)] (28)
was isolated. The formation of 28 may be due to the
presence of trace amount of moisture, which hydrolyses
23 followed by the protonation of phenolic oxygen. The
31P NMR spectrum of 28 shows doublet of doublets at
2
63.9 and 45.2 ppm with a JPRuP coupling of 37.8 Hz.
Further support for the formation of the complex 28
comes from its 1H NMR spectrum, micro analytical
and mass spectral data.
3. Summary
We have demonstrated the versatility of phosphines
containing ether functionality which readily form com-
plexes with various transition metal organometallic
derivatives. These ligands exhibit both monodentate
and bidentate modes of coordination. Group 6 metal
carbonyls and Pt(II) derivatives form complexes with
free ethereal oxygen ends, whereas Rh(I) derivatives
form both chelate and monodentate complexes. Ether
The reaction of metalloligand 23 with Ni(CO)2-
(PPh3)2 in CH2Cl2 at room temperature yielded [(OC)2-
Ni(l-PPh2C6H4O-o)2ZrCp2] (26). The 31P NMR
O
O
Ph
O
O
Ph
O
O
P
O
O
O
O
O
P
P
P
I
Cl
Cl
[Pt(COD)I2]
[Pd(COD)Cl2]
Pd
Ph
Pt
I
P
Ph
O
O
O
O
Ph
O
O
O
O
O
1
22
20
Scheme 3.

S. Priya et al. / Journal of Organometallic Chemistry 689 (2004) 3335–3349
3343
Table 7
1H and 31P NMR data of compounds 1–21
Compounds
dCH
dCH
dP
JPM
Dd
3
2
PPh2C6H4OCH2CH3 (1)
PPh(C6H4OCH2CH3)2 (2)
–
–
–
–
ꢀ16.0
ꢀ26.1
70.7
–
–
–
–
[Cr(CO)4(PPh2C6H4OCH2CH3)2] (3)
[Cr(CO)4{PPh(C6H4OCH2CH3)2}2] (4)
[Mo(CO)4(PPh2C6H4OCH2CH3)2] (5)
[W(CO)4(PPh2C6H4OCH2CH3)2] (6)
[W(CO)4{PPh(C6H4OCH2CH3)2}2] (7)
[Mo(CO)5(PPh2C6H4OCH2CH3)] (8)
[Mo(CO)5{PPh(C6H4OCH2CH3)2}] (9)
[Ru(Ph2PC6H4O)3] (10)
3.05
3.19
3.10
3.23
3.09
3.09
3.12
–
4.89
5.11
4.99
5.14
4.85
4.99
5.02
–
–
86.7
94.4
49.7
34.2
43.9
45.5
48.7
76.2
75.5
39.0
64.4
50.0
68.3
33.7
–
–
18.2
17.8
229
259
–
29.5
22.6
–
49.1
59.5
–
[Rh(CO)Cl(PPh2C6H4OCH2OCH3)] (12)
[Rh(COD)(PPh2C6H4OCH2OCH3)Cl] (13),
[Rh(COD)(PPh2C6H4OCH2OCH3)]2 Æ 2Cl (14)
[Rh(COD)(PPh2C6H4OCH2OCH3)]ÆBF4 (15)
[Pd(PPh2C6H4O)(PPh2C6H4OH)Cl] (16)
[Pd(PPh2C6H4O)2] (17)
1.25
3.37
1.38
1.43
–
2.17
5.07
2.59
2.19
–
174
150
142
159
12.3a
–
23.0
48.4
34.0
20.8(d), 47.1(d)
43.7
45.4
47.9, 74.2
70.8
61.4
–
–
[Pd(PPh2C6H4OCH2OCH3)2] Æ 2BF4 (19)
[Pd{Ph(C6H4OCH2OCH3)2}2Cl2] (20)
[Pt(PPh2C6H4OCH2OCH3)2I2] (21)
[Pt{PPh(C6H4OCH2OCH3)2}2I2] (22)
0.90
3.05
3.10
3.11
2.20
4.85
4.94
4.94
–
14.3
5.6
–
40.4
21.6
2565
2611
1.7
27.8
a
2JPP; d in ppm and J in Hz.
CO
Ph
2P
CO
CO
O
O
MO(CO)6
Zr
Mo
CO
Ph
2P
24
CO
P
O
CO
Ph2
Ph2
PPh2
PPh2
O
Zr
Re
Re(CO)3Br(CH3CN)2
Zr
O
Br
P
O
CO
23
25
Ph2
Ni
Ni(CO)2(PPh3)2
P
O
O
CO
CO
Zr
P
Ph2
26
Scheme 4.
linkage gets cleaved in case of Ru(III), Ru(II) and Pd(II)
derivatives. This could be attributed to the presence of
additional ꢀOCH2ꢁ group, which facilitates the metathet-
ical elimination of methoxymethyl chloride. The crystal
structure of the palladium complex shows extensive
hydrogen bonding between the co-crystallized phospho-
nium salt and the metal moiety. Besides the cleavage, the
quaternization of phosphorus center was also observed
in the formation of the phosphonium salt (18) which
was found co-crystallized with palladium complex 16.

3344
S. Priya et al. / Journal of Organometallic Chemistry 689 (2004) 3335–3349
Ph2
M
P
O
Cl
Cl
Zr
O
P
Ph2
Ru
CpRuCl(PPh3)2
PPh2
PPh2
PPh2
O
O
Zr
[M(COD)Cl2]
Ph2P
+
O
OH
28
Ph
Ph2
P
23
P 2
M
O
O
M = Pd, 17
Pt, 27
Scheme 5.
Interestingly, the formation of phosphonium salt, pre-
sumably from the cleavage product, CH3OCH2Cl, ap-
pears to take place only in the presence of a metal. No
such reaction was observed in the deprotection reactions
of ligands 1 or 2 with anhydrous HCl where the byprod-
uct is also CH3OCH2Cl. The extensive hydrogen-bond-
ing interactions between the phosphonium salt and the
hydroxyl group on the palladium bound phosphinophe-
nol of complex 17 prevented the formation of complex
18 through cyclization.
The metalloligand Cp2Zr(OC6H4PPh2)2 obtained
from phosphinophenol readily forms heterobimetallic
complexes, [(OC)4Mo(l-PPh2C6H4O-o)2ZrCp2], mer-
[(OC)3Re(l-PPh2C6H4O-o)2ZrCp2] and [(OC)2Ni(l-
PPh2C6H4O-o)2ZrCp2] with corresponding metal carbonyl
derivatives. Its reactions with the metal halides leads to
trans metallation and formation of chelate complexes
[M(Ph2PC6H4O-o)2] (M = Pd, Pt) and [CpRu(PPh2-
C6H4OH-o)(PPh2C6H4O-o)]. The Group 6 metal deriva-
tives with free ether ends can be used as metallo ligands
to prepare homo- and heterobimetallic complexes. The
Rh(I) and heterobimetallic complexes reported here give
scope for utilization as catalysts in various organic
transformations. The research in this direction is in pro-
gress in our laboratory.
[14]) and W(CO)4(pip)2 [15] M(COD)Cl2 (M = Pd [16],
Pt [17]), [Rh(CO)2Cl]2 [18] and [Rh(COD)Cl]2 [19] were
1
prepared according to the literature procedures. The H
and 31P NMR spectra were recorded using VXR 300 S
and Bruker spectrometers; Me4Si was used as internal
1
standard for the H NMR and 85% H3PO4 as external
standard for the 31P NMR. Positive values indicate
downfield shifts. IR spectra were recorded on a Nicolet
Impact 400 FT IR instrument in KBr disks. Microanal-
yses were performed on a Carlo Erba model 1112 ele-
mental analyser. The FAB mass spectra were recorded
on JEOL SX 102/DA-6000 and Q-Tof micro (YA-105)
mass spectrometer/Data system using Argon/Xenon (6
kV, 10 mA) as FAB gas. Melting points were recorded
in capillary tubes and are uncorrected.
4.1. trans-[Cr(CO)4(RPPhC6H4OCH2OCH3-o)2] (R = Ph,
3; C6H4OCH2OCH3-o, 4)
A mixture of Cr(CO)4(NBD) (0.035 g, 0.136 mmol)
and RPPhC6H4OCH2OCH3-o (0.270 mmol) in n-hexane
(10 ml) was heated to reflux for 9 h. The reaction mix-
ture became turbid and the yellow solid precipitated
out was filtered and the precipitate was dried and re-
crystallized from CH2Cl2–diethyl ether (2:1) mixture to
obtain pure products.
4. Experimental
4.2. trans-[Cr(CO)4(PPh2C6H4OCH2OCH3-o)2] (3)
All manipulations were performed under rigorously
anaerobic conditions using Schlenk techniques. All the
solvents were purified by conventional procedures and
distilled prior to use. The phosphine ethers Ph2PC6H4O-
CH2OCH3-o [7] and PhP(C6H4OCH2OCH3-o)2 [7] and
metal precursors, M(CO)4(NBD) (M = Mo [13], Cr
Yield: 59% (0.097 g, 0.113 mmol), m.p.: 152–156 ꢁC
(dec.). Anal. Calc. for C44H38O8P2Cr: C 65.35; H 4.74.
Found: C 65.14; H 4.62%. FTIR (KBr disk) cmꢀ1
:
1
m
CO: 1887 vs. H NMR (CDCl3): d 3.05 (s, CH3, 3H),
4.89 (s, CH2, 2H), 6.64–7.65 (m, phenyl, 14H). 31P{1H}
NMR (CDCl3): d 70.7 (s).

S. Priya et al. / Journal of Organometallic Chemistry 689 (2004) 3335–3349
3345
4.3. trans-[Cr(CO)4{PPh(C6H4OCH2OCH3-o)2}2] (4)
4.8. Mo(CO)5(RPPhC6H4OCH2OCH3-o) (R = Ph, 8;
C6H4OCH2OCH3-o, 9)
Yield: 63% (0.091 g, 0.098 mmol), m.p.: 128–130 ꢁC
(dec.). Anal. Calc. for C48H46O12P2Cr: C 62.07; H
4.99. Found: C 61.92; H 5.17%. FTIR (KBr disk)
A mixture of Mo(CO)6 (0.05 g, 0.176 mmol) and
PhPC6H4OCH2OCH3-o (0.176 mmol) in benzene (10
ml) was refluxed for 20 h. The solvent was evaporated un-
der reduced pressure and the residue obtained was ex-
tracted with n-hexane (3 · 5 ml). The solution was
filtered through celite, the yellow filtrate was concentrated
to 4 ml and cooled at 0 ꢁC to give crystalline products.
1
cmꢀ1: mCO: 1877 vs. H NMR (CDCl3): 3.19 (s, CH3,
6H), 5.11 (s, CH2, 4H), 6.64–7.65 (m, phenyl, 13H).
31P{1H} NMR (CDCl3): d 68.3 (s).
4.4. Mo(CO)4(PPh2C6H4OCH2OCH3-o)2 (5)
A solution of Mo(CO)4(NBD) (0.04 g, 0.130 mmol)
in n-hexane (5 ml) was added to Ph2PC6H4O-
CH2OCH3-o (0.088 g, 0.260 mmol) in n-hexane (5 ml)
and was heated to reflux for 2 h. The yellow solid precip-
itated out from the reaction mixture was separated by
filtration and the residue was washed with n-hexane
and dried under vacuum. Yield: 85% (0.097 g, 0.113
mmol), m.p.: 154–156 ꢁC (dec.). Anal. Calc. for
C44H38O8P2Mo Æ CH2Cl2: C 57.65; H 4.30. Found: C
57.28; H 4.40%. FTIR (KBr disk) cmꢀ1: mCO: 2014 s,
4.9. Mo(CO)5(PPh2C6H4OCH2OCH3-o) (8)
Yield: 48% (0.052 g, 0.093 mmol), m.p.: 134–136 ꢁC
(dec.). Anal. Calc. for C25H19O7PMo: C 53.79; H 3.43.
Found: C 53.68; H 3.55%. FTIR (KBr disk) cmꢀ1
:
1
m
(s, OCH3, 3H), 4.99 (s, OCH2, 2H), 6.87–7.62 (m, phe-
CO: 2071 s, 1931 br and vs. H NMR (CDCl3): d 3.09
nyl, 14H). 31P{1H} NMR (CDCl3): d 29.5 (s).
4.10. Mo(CO)5{PPh(C6H4OCH2OCH3-o)2} (9)
1
1916 vs, 1883 vs. H NMR (CDCl3): d 3.10 (s, CH3,
3H), 4.99 (s, CH2, 2H), 6.69–7.73 (m, phenyl, 14H).
31P{1H} NMR (CDCl3): d 33.7 (s).
Yield: 81% (0.095 g, 0.154 mmol), m.p.: 114–116 ꢁC
(dec.). Anal. Calc. for C27H23O9PMo: C 52.45; H 3.75.
Found: C 52.26; H 3.68%. FTIR (KBr disk) cmꢀ1
:
1
4.5. cis-[W(CO)4(RPPhC6H4OCH2OCH3-o)2] (R = Ph,
6; C6H4OCH2OCH3-o, 7)
m
CO: 2066 s, 1943 br and vs. H NMR (CDCl3): d 3.12
2
(s, OCH3, 6H), 5.02 (AB q, OCH2, JHH = 7.12 Hz,
4H), 6.95–7.62 (m, phenyl, 13H). 31P{1H} NMR
(CDCl3): d 22.6 (s).
To a solution of RPhPC6H4OCH2OCH3-o (0.214
mmol) in CH2Cl2 (5 ml) was added a solution of
W(CO)4(NC5H11)2 (0.050 g, 0.102 mmol) also in CH2Cl2
(5 ml) at room temperature and the reaction mixture was
stirred at room temperature for 12 h. The solvent was
evaporated from the reaction mixture under reduced pres-
sure and the residue obtained was washed with n-hexane
(5 · 5 ml) and re-crystallized from a mixture of CH2Cl2-
n-hexane (1:1) to obtain analytically pure product.
4.11. [Ru(OC6H4PPh2)3] (10)
To a refluxing solution of Ph2PC6H4OCH2OCH3
(0.186 g, 0.570 mmol) in 2-methoxyethanol (5 ml) was
added RuCl3 Æ 3H2O (0.05 g, 0.190 mmol) in water (2
ml) and the reaction mixture was refluxed for 2 h. The
reaction mixture was filtered to separate a blue crystal-
line solid and further product was obtained from the
mother liquor on concentration and cooling. Single crys-
tals of the product were grown by slow evaporation of a
CH2Cl2 solution at room temperature. Yield: 70%
(0,135 g, 0.130 mmol), m.p.: above 250 ꢁC (dec.). Anal.
Calc. for C54H42P3O3Ru Æ CH2Cl2: C 64.90; H 4.36.
4.6. cis-[W(CO)4(PPh2C6H4OCH2OCH3-o)2] (6)
Yield: 85% (0.085 g, 0.090 mmol), m.p.: 154–157 ꢁC
(dec.). Anal. Calc. for C44H38O8P2W: C 56.19; H 4.07.
Found: C 56.29; H 3.98%. FTIR (KBr disk) cmꢀ1
m
:
CO: 2010 s, 1927 vs, 1876 vs, 1774s. 1H NMR
Found: C 64.68; H 4.26%. H NMR (CDCl3): 6.0–8.7
(m, phenyl) (broad). 31P{1H} NMR (CDCl3): broad
peak centered at 49 ppm.
1
(CD3COCD3): 3.23 (s, CH3, 3H), 5.14 (s, CH2, 2H),
7.08–7.82 (m, phenyl, 14H). 31P{1H} NMR
(CD3COCD3): d 18.2 (1JWP = 229.2 Hz).
4.12. CpRu(OC6H4PPh2)(PPh3)2 (11)
4.7. cis-[W(CO)4{PPh (C6H4OCH2OCH3-o)2}2] (7)
To a solution of CpRuCl(PPh3)2 (0.05 g, 0.068 mmol)
in CH2Cl2 (5 ml) was added a CH2Cl2 (5 ml) solution of
1 (0.022 g, 0.068 mmol) and the reaction mixture was
stirred at room temperature for 6 h. The resulting solu-
tion was evaporated under reduced pressure and the res-
idue was with n-hexane (3 · 5 ml), the residue was
dissolved in toluene (10 ml) and the solution on storing
Yield: 84% (0.095 g, 0.080 mmol), m.p.: 117–120 ꢁC
(dec.). Anal. Calc. for C48H46O12P2W: C 54.33; H 4.37.
Found: C 53.92; H 4.47%. FTIR (KBr disk) cmꢀ1: mCO
:
1
2009 s, 1912 vs, 1876 vs, 1850s. H NMR (CDCl3): d
3.09 (s, CH3, 6H), 4.85 (s, CH2, 4H), 6.82–7.42 (m, phenyl,
13H). 31P{1H} NMR (CDCl3): d 17.8 (1JWP = 259.2 Hz).

3346
S. Priya et al. / Journal of Organometallic Chemistry 689 (2004) 3335–3349
at 0 ꢁC gave orange-red crystalline product. Yield: 40%
(0.021 g, 0.029 mmol), m.p.: 168–170 ꢁC (dec.). Anal.
Calc. for C41H34OP2Ru: C 69.78; H 4.86. Found: C
CH2Cl2/petroleum ether mixture (2:1) at 0 ꢁC to give
crystalline product. Yield: 72% (0.045 g, 0.07 mmol),
m.p.: 166–170 ꢁC (dec.). Anal. Calc. for C28H31O2
PRhBF4: C 54.22; H 5.04. Found: C 53.99; H 4.95%.
1H NMR (CDCl3): d 0.83–1.31 (m, CH2 (COD), 8H),
1.43 (s, OCH3, 3H), 2.19 (s, OCH2, 2H), 2.47 (br,
‚CH (COD), 2H), 3.81 (br, ‚CH (COD), 1H), 5.71
(br, ‚CH (COD), 1H), 6.83–7.74 (m, phenyl, 14H).
31P{1H} NMR (CDCl3): d 34.0 (d, 1JRhP = 159.2 Hz).
1
69.03; H 4.67%. H NMR (CDCl3): d 4.10 (s, C5H5,
5H), 6.85–7.04 (m, phenyl, 4H), 7.11–7.72 (m, PPh,
25H). 31P{1H} NMR (CDCl3): d 44.2 (d, PPh3,
2
2JPRuP = 36.4 Hz), 57.4 (d, PPh2, JPRuP = 36.4 Hz).
MS (FAB): 706 (M+ + 1).
4.13. [Rh(CO)(PPh2C6H4OCH2OCH3)Cl] (12)
4.16. Reaction of [Pd(COD)Cl2] with 1
A mixture of [Rh(CO)2Cl]2 (0.030 g, 0.077 mmol) and
Ph2PC6H4OCH2OCH3 (0.05 g, 0.154 mmol) in CH3CN
(10 ml) was stirred at reflux for 4 h. The resulting yellow
solution was evaporated under reduced pressure and the
residue was crystallized from a CH2Cl2-n-hexane (2:1)
mixture at ꢀ10 ꢁC to get the product of analytical purity.
Yield: 76% (0.057g, 0.117 mmol), m.p.: 195–198 ꢁC
(dec.). Anal. Calc. for C21H19O3PRhCl, C 51.61; H
To a stirred solution of Ph2PC6H4OCH2OCH3 (0.068
g, 0.210 mmol) in CH2Cl2 (5 ml) was added drop-wise a
solution of cis-Pd(COD)Cl2 (0.030 g, 0.210 mmol) also
in CH2Cl2 (5 ml) at room temperature and the reaction
mixture was stirred at room temperature for 8 h. Solvent
was evaporated under reduced pressure from the reac-
tion mixture and the residue obtained was washed with
n-hexane (3 · 5 ml). The phosphorus NMR of the crude
solid revealed the presence of mixture of products
[31P{1H} NMR (CDCl3): d 20.8 (d), 47.1(d) (PPh2,
2JPP = 12.3 Hz); 16.1 (s); 43.7 (s)]. Recrystallization of
this mixture at room temperature from CH2Cl2/diethyl
ether (2:1) mixture at room temperature, afforded yellow
crystalline [Pd(PPh2C6H4O)2] (17) in the first crop and
from the mother liquor on cooling yellow crystals of
the complex 16 co-crystallized with Ph2P+(CH2OCH3)
(C6H4OH)Cl (18).
3.92. Found: C 51.47; H 3.87%. FTIR (KBr disk) cmꢀ1
:
1
mCO: 1956 vs. H NMR (CDCl3): d 1.25 (s, OCH3, 3H),
2.17 (s, OCH2, 2H), 7.26–7.76 (m, phenyl, 14H).
31P{1H} NMR (CDCl3): d 59.5 (d, 1JRhP = 173.8 Hz).
4.14. [RhCl(COD)(PPh2C6H4OCH2OCH3)] (13)
A mixture of [Rh(COD)Cl]2 (0.025 g, 0.051 mmol) and
PPh2C6H4OCH2CH3 (0.033 g, 0.104 mmol) in CH3CN
(10 ml) was stirred with heating for 10 h. The reaction
mixture was cooled, the solvent was evaporated under re-
duced pressure and the residue obtained was washed with
n-hexane (5 · 3 ml) and dried to get yellow solid of ana-
lytical purity. Yield: 67% (0.050 g, 0.068 mmol), m.p.:
149–155 ꢁC (dec.). Anal. Calc. for C28H31O2PRh-
Cl Æ 2CH2Cl2: C 48.77; H 4.78. Found: C 48.34; H
4.57%. 1H NMR (CDCl3): d 1.64–2.47 (m, CH2 (COD),
8H), 3.37 (br s, OCH3 and ‚CH (COD), 4H), 4.23 (br,
‚CH (COD), 1H), 5.07 (s, OCH2, 2H), 5.43 (s, ‚CH
(COD), 2H), 6.93–7.82 (m, phenyl, 14H). 31P{1H}
NMR (CDCl3): d 23.0 (d, 1JRhP = 149.6 Hz).
4.17. [PdCl(PPh2C6H4OH)(PPh2C6H4O)] (16)
Yield: 40% (0.044 g, 0.042 mmol), m.p.: 155–158 ꢁC.
Anal. Calc. for C36H29O2P2PdCl2. C20H20O2PCl, C
63.68; H 4.67. Found: C 63.38; H 4.61%. 1H NMR
(CDCl3): d 1.95 (s, CH3, 3H), 3.51 (br s, OCH2, 2H),
6.45–7.98 (m, phenyl, 28H). 31P{1H} NMR (CDCl3): d
2
20.8 (d), 47.1(d) (P Ph2, JPP = 12.3 Hz); 16.0 (s).
[Pd(g2-PPh2C6H4O)2] (17). Yield: 21% (0.015 g, 0.022
mmol), m.p.: 225–227 ꢁC. Anal. Calc. for
C37.5H31Cl3O2P2Pd: C 57.13; H 3.96. Found: C 57.25;
The 31P NMR spectrum of the crude sample showed two
1
peaks [31P{1H} NMR (CDCl3): d 23.0 (d, JRhP = 149.6
Hz), 48.4 (d, JRhP = 141.9 Hz)]. The additional doublet
H 4.01%. 31P{1H} NMR (CDCl3): d 43.7 (s). MS
1
(FAB): 661 (M+ + 1).
at 48.4 ppm could be eliminated by crystallization and the
presence of that may be attributed to the complex
[Rh(COD)(PPh2C6H4OCH2CH3–jP, jO)]2Cl2 (14).
4.18. [Pd(PPh2C6H4OCH2OCH3)2](BF4)2 (19)
To a stirring solution of Ph2PC6H4OCH2O–CH3
(0.068 g, 0.210 mmol) and AgBF4 (0.041 g, 0.210 mmol)
in CH2Cl2 (5 ml) was added cis-Pd(COD)Cl2 (0.030 g,
0.210 mmol) also in CH2Cl2 (5 ml) at room temperature.
The reaction mixture was stirred at room temperature
for 6 h. The resulting solution was passed through celite,
the solvent was evaporated in vacuo and the residue ob-
tained was washed with n-hexane (3 · 5 ml). The yellow
solid was crystallized from a CH2Cl2/n-hexane (2:1) mix-
ture at 0 ꢁC to give bright yellow crystalline solid 19.
4.15. [Rh(COD)(PPh2C6H4OCH2OCH3)]BF4 (15)
To a mixture of [Rh(COD)Cl]2 (0.025 g, 0.051 mmol)
and PPh2C6H4OCH2CH3 (0.033 g, 0.104 mmol) in ace-
tone (10 ml), AgBF4 (0.0197 g, 0.100 mmol) was added
and the reaction mixture was stirred at room temperature
for 6 h and passed through celite. The filtrate was evapo-
rated under reduced pressure and the residue was washed
with petroleum ether (3 · 5 ml) and crystallized from a

S. Priya et al. / Journal of Organometallic Chemistry 689 (2004) 3335–3349
3347
Yield: 65% (0.063 g, 0.068 mmol), m.p.: 208–211 ꢁC.
Anal. Calc. for C40H38O4P2PdB2F8: C 51.96; H 4.14.
Found: C 51.83; H 4.22%. H NMR (CDCl3): d 0.90
(s, OCH3, 3H), 2.20 (s, OCH2, 2H), 6.78–7.82 (m, phe-
nyl, 14H). 31P{1H} NMR (CDCl3): d 45.4 (s). MS
(FAB): 927 (M+ + 2).
4.23. (OC)4Mo(l-PPh2C6H4O)2ZrCp2 (24)
1
To a solution of Cp2Zr(OC6H4PPh2)2 (0.088 g, 0.11
mmol) in benzene (5 ml) was added Mo(CO)6 (0.03 g,
0.11 mmol) also in benzene (5 ml) and the reaction mix-
ture was stirred at reflux condition for 10 h. The solvent
was evaporated under reduced pressure and the residue
obtained was extracted with petroleum ether (15 ml) and
the solution was passed through celite. The filtrate on
concentration and cooling gave yellow crystalline prod-
uct. Yield: 45% (0.05 g, 0.051 mmol), m.p.: 160–164 ꢁC
(dec.). Anal. Calc. for C50H38O6P2MoZr: C 61.03; H
3.89. Found: C 61.18; H 3.96%. FTIR (KBr disk)
4.19. [PdCl2{PPh(C6H4OCH2OCH3)2}2] (20)
To a stirring solution of PhP(C6H4OCH2OCH3)2
(0.080 g, 0.210 mmol) in CH2Cl2 (5 ml) was added a
solution of cis-Pd(COD)Cl2 (0.030 g, 0.210 mmol) also
in CH2Cl2 (5 ml) at room temperature and the resulting
yellow solution was stirred at room temperature for 6 h.
Solvent was evaporated under reduced pressure from the
reaction mixture, the residue was washed with n–hexane
(3 · 5 ml) and was crystallized from CH2Cl2/n-hexane
(2:1) mixture at 0 ꢁC to give a bright yellow crystalline
solid. Yield: 61% (0.067 g, 0.064 mmol), m.p.: 220–
222 ꢁC. Anal. Calc. for C44H46O4P2PdCl2 Æ 2CH2Cl2:
cmꢀ1: mCO: 2014 m, 1922 s, 1875 s, 1842 s. H NMR
(CDCl3): 5.81 (s, C5H5, 5H), 6.79–7.19 (m, phenyl,
4H), 7.26–7.92 (m, PPh2, 10H). 31P{1H} NMR (CDCl3):
39.5(s). MS (FAB): 988 (M+).
1
4.24. mer-(OC)3ReBr(l-PPh2C6H4O)2ZrCp2 (25)
1
C 52.72; H 4.80. Found: C 52.79; H 4.66%. H NMR
To a stirring solution of Cp2Zr(OC6H4PPh2)2 (0.072 g,
0.09 mmol) in CH2Cl2 (7 ml) was added drop wise a solu-
tion of fac-[Re(CO)3(CH3CN)2Br] (0.04 g, 0.09 mmol)
also in CH2Cl2 (5 ml) at room temperature and the reac-
tion mixture was allowed to stir at room temperature for
3 h. The solution was concentrated, diluted with n-hexane
(3 ml) and cooled to 0 ꢁC to give crystalline product of 24.
Yield: 83% (0.087 g, 0.076 mmol). Anal. Calc. for
C49H38BrO5P2ReZr: C 52.26; H 3.40. Found: C 52.12;
H 3.31%. FTIR (KBr disk) cmꢀ1: mCO: 2029 vs, 1949 s,
(CDCl3): d 3.05 (s, OCH3, 3H), 4.85 (s, OCH2, 2H),
6.93–7.83 (m, phenyl, 13H). 31P{1H} NMR (CDCl3): d
14.3 (s).
4.20. [PtI2(P(R)PhC6H4OCH2OCH3)2] (R = Ph, 21;
C6H4OCH2CH3, 22)
To a stirring solution of cis-Pt(COD)I2 (0.030 g,
0.054 mmol) in CH2Cl2 (5 ml), PhRPC6H4OCH2OCH3
(0.108 mmol) in CH2Cl2 (5 ml) was added at room
temperature and the reaction mixture was stirred at
room temperature for 6 h. The solvent was evaporated
from the reaction mixture under reduced pressure and
the residue obtained was washed with n-hexane (3 · 5
ml) and re-crystallized from CH2Cl2/n-hexane (2:1)
mixture at 0 ꢁC to give a bright yellow crystalline
product.
1
1899 vs. H NMR (CDCl3): d 6.37 (s, C5H5, 5H), 6.48–
6.82 (m, phenyl, 4H), 7.03–7.61 (m, PPh2, 14H).
31P{1H} NMR (CDCl3): d 9.5 (d), 26.5 (d); (2JPReP = 29.7
Hz.). MS (FAB): 1123.9 (M+).
4.25. (OC)2Ni(l-PPh2C6H4O)2ZrCp2 (26)
To a solution of Cp2Zr(OC6H4PPh2)2 (0.048 g, 0.06
mmol) in CH2Cl2 (5 ml) was added drop wise a solution
of Ni(CO)2(PPh3)2 (0.04 g, 0.60 mmol) also in CH2Cl2 (5
ml) and the reaction mixture was stirred at room temper-
ature for 6 h. The solvent was removed under reduced
pressure and the residue obtained was washed with n-hex-
ane (3 · 5 ml) and re-crystallized from CH2Cl2–petroleum
ether (2:1) mixture at ꢀ5 ꢁC to get crystalline product of
25. Yield: 91% (0.05 g, 0.056 mmol), m.p.: 225–228 ꢁC
(dec.). Anal. Calc. for C48H38BrO4P2NiZr: C 59.40; H
4.21. [PtI2(PPh2C6H4OCH2OCH3)2] (21)
Yield: 59% (0.040g, 0.032 mmol), m.p.: 228–230 ꢁC
(dec.). Anal. Calc. for C40H38O4P2PtI2 Æ 2CH2Cl2:
C39.93; H 3.35. Found: C 39.58; H 2.85%. H NMR
1
(CDCl3): d 3.10 (s, OCH3, 3H), 4.94 (s, OCH2, 2H),
6.92–7.87 (m, phenyl, 14H). 31P{1H} NMR (CDCl3): d
5.6 (1JPtP = 2565 Hz).
3.95. Found: C 59.22; H 3.82%. FTIR (KBr disk) cmꢀ1
:
CO: 2004 s, 1948 s. H NMR (CDCl3): 6.72 (s, C5H5,
1
4.22. [PtI2{PPh(C6H4OCH2OCH3)2}2] (22)
m
5H), 6.93–7.69 (m, phenyl, 14H). 31P{1H} NMR
Yield: 68% (0.048g, 0.036 mmol), m.p.: 198–201 ꢁC
(dec.). Anal. Calc. for C40H46O8P2PtI2: C 41.21; H
(CDCl3): 34.4 (s). MS (FAB): 890 (M+).
1
3.97. Found: C 41.04; H 3.99%. H NMR (CDCl3): d
3.11 (s, OCH3, 3H), 4.94 (s, OCH2, 2H), 6.89–7.86 (m,
4.26. Pd{(OC6H4PPh2)2} (17)
phenyl, 13H). 31P{1H} NMR (CDCl3):
(1JPtP = 2611 Hz).
d
1.7
A mixture of cis-[PdCl2(COD)] (0.03 g, 0.105 mmol)
and Cp2Zr(OC6H4PPh2)2 (0.082 g, 0.11 mmol) was

3348
S. Priya et al. / Journal of Organometallic Chemistry 689 (2004) 3335–3349
dissolved in 7 ml of dichloromethane and the solution
was stirred at room temperature for 6 h. Evaporation
of the solution under vacuo yielded sticky residue, which
was washed with petroleum ether twice to remove cyclo-
octadiene. The resultant crude bright-yellow solid ob-
tained was crystallized from a CH2Cl2–petroleum ether
(3:1) mixture. Yield: 70% (0.07 g, 0.073 mmol), m.p.:
filtrate on storing at 0 ꢁC gave orange-red crystalline
product. Yield: 78% (0.038 g, 0.054 mmol), m.p.: 168–
170 ꢁC (dec.). Anal. Calc. for C41H34OP2Ru: C 69.78;
1
H 4.86. Found: C 69.03; H 4.67%. H NMR (CDCl3):
d 4.10 (s, C5H5, 5H), 6.85–7.04 (m, phenyl, 4H), 7.11–
7.72 (m, PPh, 25H). 31P{1H} NMR (CDCl3): d 44.2
2
Ph3, JPRuP = 36.4 Hz), 57.4 (d,
(d,
P
P
Ph2,
1
225–227 ꢁC (dec.). H NMR (CDCl3): d 6.57–6.91 (m,
2JPRuP = 36.4 Hz). MS (FAB): 706 (M+ + 1).
phenyl, 4H), 7.03–8.71 (m, phenyl, 10H). 31P{1H}
NMR (CDCl3): d 43.7 (s).
5. X-ray crystal structure analysis of 8, 9, 10, 16 and 17
4.27. Pt{(OC6H4PPh2)2} (27)
Crystals of compounds 8 and 9 are mounted on Pyrex
filaments with epoxy resin. An Enraf-Nonius CAD-4
diffractometer was used for the unit cell determination
and intensity data collection. The initially obtained unit
cell parameters were refined by accurately centering
randomly selected reflections in the 2h ranges given in
Table 1. General procedures for crystal alignment
and collection of intensity data on the Enraf-Nonius
CAD-4 diffractometer have been published [20]. Peri-
odic monitoring of check reflections showed stability
of the intensity data. Details of the crystal and data col-
lection are given in Table 1. The data were corrected for
Lorentz and polarization effects [21] and an empirical
correction for absorption was applied using w scan data
from several reflections with v near 90ꢁ. The metal atom
positions were obtained from sharpened Patterson func-
tions and the remainder of the structures developed by
successive cycles of full-matrix, least-squares refinement
followed by calculation of a difference map. Hydrogen
atoms were placed in calculated positions (C–H = 0.95
A mixture of cis-[PtCl2(COD)] (0.03 g, 0.08 mmol)
and Cp2Zr(OC6H4PPh2)2 (0.062 g, 0.08 mmol) was dis-
solved in 5 ml of dichloromethane and the solution was
stirred for 6 h at room temperature. Evaporation of the
reaction mixture under vacuo yielded sticky white resi-
due, which was washed with diethyl ether (2 · 4 ml).
The resultant crude bright-white solid was dissolved in
a mixture of CH2Cl2–petroleum ether (3:1) mixture to
give analytically pure sample of 27. Yield: 70% (0.058
g, 0.053 mmol). Anal. Calc. for C36H28O2P2Pt: C
62.87; H 4.10. Found: C 62.82; H 4.12%. 1H NMR
3
(CDCl3): d 6.49 (t, O–C6H4–P, JHH = 8.9 Hz, 2H),
6.88 (t, O–C6H4–P, JHH = 8.9 Hz, 2H), 7.02–7.36 (m,
3
PPh, 10H). 31P{1H} NMR (CDCl3):
1JPtP = 3540 Hz).
d 19.3 (s,
4.28. CpRu(PPh2C6H4O)(PPh2C6H4OH) (28)
To a solution of 23 (0.053 g, 0.068 mmol) in CH2Cl2
(5 ml) was added a solution of CpRuCl(PPh3)2 (0.05 g,
0.068 mmol) also in CH2Cl2 (5 ml) and the reaction mix-
ture was stirred at room temperature for 12 h. The solu-
tion was evaporated under reduced pressure and the
residue obtained was dissolved in diethyl ether (10 ml),
which on cooling gave orange-red crystalline product
of 27. Yield: 61% (0.031 g, 0.043 mmol), m.p.: 177–
180 ꢁC (dec.). Anal. Calc. for C41H34O2P2Ru: C 68.23;
H 4.75. Found: C 69.01; H 5.18%. FTIR (KBr disk)
cmꢀ1: mOH: 3404 br s. 1H NMR (CDCl3): d 4.22 (s,
C5H5, 5H), 6.29–6.92 (m, phenyl, 8H), 7.02–7.45 (m,
PPh, 20H). 31P{1H} NMR (CDCl3): d 45.2 (d, PPh2,
˚
A) with isotropic displacement parameters 1.2 times
those of the attached atom and included as riding contri-
butions. The calculations were performed with the
SHELXTL PLUS [22] program package. Crystals of com-
pounds 10, 16, 17 and 18 were mounted in a Cryo-
loopTM with a drop of Paratone oil and placed in the
cold nitrogen stream of the KryoflexTM attachment of
a Bruker APEX CCD diffractometer. A full sphere of
data was collected using 606 scans in x (0.3ꢁ per scan)
at / = 0, 120 and 240o using the SMART software pack-
age [23]. The raw data were reduced to F2 values using
the SAINT+ software [24] and a global refinement of unit
cell parameters employing all reflections chosen from
the full data set was performed. Multiple measurements
of equivalent reflections provided the basis for an empir-
ical absorption correction as well as a correction for any
crystal deterioration during the data collection (SADABS
[25]). The structure of 10 was solved by direct methods
[26] while the position of metal atom was obtained from
a sharpened Patterson function for the complexes 16
and 17. In the latter case, the structure was developed
as described for 8 and 9. Both structures were refined
by full-matrix least-squares procedures using the SHEL-
XTL program package [27]. Hydrogen atoms were
2
2JPRuP = 37.8 Hz), 63.9 (d, PPh2, JPRuP = 37.8 Hz).
MS (FAB): 722 (M+ + 1), 705 (M+–OH).
4.29. CpRu(PPh2C6H4O)(PPh3)2 (11)
To a solution of CpRuCl(PPh3)2 (0.05 g, 0.068 mmol)
in CH2Cl2 (5 ml) was added a CH2Cl2 (5 ml) solution of
Ph2PC6H4OH (0.038 g, 0.068 mmol) and the reaction
mixture was stirred at room temperature for 6 h. The
resulting solution was evaporated under reduced pres-
sure and the residue was dissolved in diethyl ether (10
ml) and the solution was passed through celite and the

S. Priya et al. / Journal of Organometallic Chemistry 689 (2004) 3335–3349
3349
(e) M.S. Balakrishna, M.G. Walawalker, J. Organomet. Chem.
628 (2001) 76;
placed in calculated positions and included as riding
contributions with isotropic displacement parameters
as described for 8 and 9.
(f) S. Priya, M.S. Balakrishna, J.T. Mague, Inorg. Chem.
Commun. 4 (2001) 437;
(g) S. Priya, M.S. Balakrishna, J.T. Mague, S.M. Mobin, Inorg.
Chem. 42 (2003) 1272;
6. Supporting information available
(h) S. Priya, M.S. Balakrishna, J.T. Mague, J. Organomet. Chem.
679 (2003) 116;
Full details of data collection and structure refine-
ment have been deposited with the Cambridge Crystal-
lography Data Centre, CCDC nos. 231483, 231484,
231485, 231481 and 231482 for compounds [Mo(CO)5-
(PPh2C6H4OCH2OCH3)](8), [Mo(CO)5{PPh(C6H4OCH2-
OCH3)2}] (9), [Ru(OC6H4PPh2)3] (10) [PdCl (PPh2C6H4-
OH)(PPh2C6H4O)] [Ph2P(CH2OCH3)(C6H4OH)Cl] (16)
and [Pd(PPh2C6H4O)2] (17), respectively. Copies of this
information may be obtained free of charge from the Direc-
tor, CCDC, 12 Union Road, Cambridge CB2 1EZ, UK
(fax: +44-1223-336033; e-mail: deposit@ccdc.cam.ac.uk or
www://http.ccdc.cam.ac.uk).
(i) S. Priya, M.S. Balakrishna, S.M. Mobin, R. McDonald, J.
Organomet. Chem. 688 (2003) 227.
[6] (a) J. Andrieu, J.-M. Camus, J. Dietz, P. Richard, R. Poli, Inorg.
Chem. 40 (2001) 1597;
(b) K. Neplechova, J. Kasparkova, O. Vrana, O. Novakova, A.
Habtemarium, B. Watchman, P.J. Sadler, V. Brabec, Mol.
Pharmacol. 56 (1999) 20;
(c) N. Margiotta, A. Habtemarium, P.J. Sadler, Angew Chem.
Int. Ed. Engl. 36 (1997) 1185;
(d) A. Habtemariam, J.A. Parkinson, N. Margiotta, T.W.
Hambley, S. Parsons, P.J. Sadler, J Chem. Soc. Dalton Trans.
(2001) 362;
(e) A.D. Burrows, M.F. Mahon, M.T. Palmer, J Chem. Soc.
Dalton Trans. (2000) 1669;
(f) E. Lindner, J. Wald, K. Eichele, R. Fawzi, J. Organomet.
Chem. 601 (2000) 220.
[7] (a) T.B. Rauchfuss, Inorg. Chem. 16 (1977) 2966;
(b) H. Luo, I. Setyawati, S.J. Rettig, C. Orvig, Inorg. Chem. 34
(1995) 2287.
Acknowledgements
We are grateful to the Department of Science and
Technology (DST), Council of Scientific and Industrial
Research (CSIR), New Delhi, India for generous sup-
port. SP thanks CSIR for JRF and SRF fellowships.
We also thank RSIC, Mumbai, Sophisticated Instru-
mentation Facility (SIF), Bangalore, the Center for
Drug Research Institute, Lucknow for spectral data
and Louisiana Board of Regents through Grant
LEQSF(2002–03)-ENH-TR-67 for purchase of the
CCD diffractometer and the Chemistry Department of
Tulane University for support of the X-ray laboratory.
[8] Y. Yamamoto, R. Sato, M. Ohshima, F. Matsuo, C. Sudoh, J.
Organomet. Chem. 489 (1995) C68.
[9] J.-F. Ma, Y. Kojima, Y. Yamamoto, J. Organomet. Chem. 616
(2000) 149.
[10] (a) C. Bolzati, F. Tisato, F. Refosco, G. Bandoli, A. Dolmella,
Inorg. Chem. 35 (1996) 16221;
(b) A.M. Trzeciak, J.J. Ziolkowski, T. Lis, R. Choukroun, J.
Organomet. Chem. 575 (1999) 87;
(c) M. Canestrari, B. Chaudret, F. Dahan, Y.-S. Huang, R.
Poilblanc, T. Chong,
1179.
J Chem. Soc. Dalton Trans. (1990)
[11] L. Miguel, M. Basso-Bert, R. Choukroun, R. Madhouni, B.
Eichhorn, M. Sanchez, M.R. Mazieres, J. Jaud, J. Organomet.
Chem. 490 (1995) 21.
[12] C.E. Jones, B.L. Shaw, B.L. Turtle, J. Chem. Soc. Dalton Trans.
(1974) 992.
[13] R.B. King, Inorg. Chem. 2 (1963) 936.
References
[14] M.A. Bennett, L. Pratt, G. Wilkinson, J. Chem. Soc. (1961)
2037.
[1] (a) A. Bader, E. Lindner, Coord. Chem. Rev. 108 (1991) 27;
(b) E. Lindner, E. Glaser, J. Organomet. Chem. 391 (1990) C37.
[2] (a) E. Lindner, U. Schober, R. Fawzi, W. Hiller, U. Englert, P.
Wegner, Chem. Ber. 120 (1987) 1621;
[15] D.J. Darensbourg, R.L. Kump, Inorg. Chem. 17 (1978) 2680.
[16] D. Drew, J.R. Doyle, Inorg. Synth. 13 (1972) 48.
[17] D.A. White, Inorg. Synth. 13 (1972) 52.
(b) T.B. Rauchfuss, F.T. Patino, D.M. Roundhill, Inorg. Chem.
14 (1975) 652.
[18] J.A. McCleverty, G. Wilkinson, Inorg. Synth. 8 (1966) 211.
[19] J. Chatt, L.M. Venanzi, J. Chem. Soc. (1957) 4735.
[20] J.T. Mague, C.L. Lloyd, Organometallics 7 (1988) 983.
[21] K. Harms, S. Wocadlo, Program to Extract Intensity Data from
Enraf-Nonius CAD-4 Files: University of Margburg, 1987.
[22] Bruker-AXS, SHELXTL PLUS version 5.1: Madison, WI,
1995.
[3] C. Nachtigal, S. Al-Gharabli, K. Eichele, E. Lindner, H.A.
Mayer, Organometallics 21 (2002) 105.
[4] (a) P. Braunstein, D. Matt, D. Nobel, J. Am. Chem. Soc. 110
(1988) 3207;
(b) W. Keim, New J. Chem. 11 (1987) 531.
[5] (a) M.S. Balakrishna, K. Ramaswamy, R.M. Abhyankar, J.
Organomet. Chem. 560 (1998) 131;
[23] Bruker-AMX SMART version 5.625: Madison, WI, 2000.
[24] Bruker-AXS SAINT+ version 6.35A: Madison, WI, 2002.
[25] G.M. Sheldrick, SADABS Version 2.05, University of Go¨ttingen,
Germany, 2002.
(b) M.S. Balakrishna, R.M. Abhyankar, J.T. Mague, J. Chem.
Soc. Dalton Trans. (1999) 1407;
(c) M.S. Balakrishna, R. Panda, J.T. Mague, Inorg. Chem. 40
(2001) 5620;
[26] G.M. Sheldrick, SHELXS97 and SHELXL97, University of Go¨ttin-
gen, Germany, 1997.
[27] Bruker-AXS SHELXTL Version 6.1: Madison, WI, 2000.
(d) M.S. Balakrishna, R.M. Abhyankar, M.G. Walawalker,
Tetrahedron Lett. 42 (2001) 2733;