Chalcogenolato-bridged cyclometallated binuclear palladium complexes: Synthesis, spectroscopy, structures of [Pd2(μ-Cl)(μ-SMes)(C10H6NMe2-C,N)2] and [Pd2(μ-SePh)2(C10H6NMe2-C,N)2]

Article abstract of DOI:10.1016/j.ica.2008.01.005

Reactions of orthometallated binuclear palladium complexes with NaER, obtained by NaBH₄ reduction of R₂E₂ in methanol, gave complexes, [Pd₂(μ-ER)₂(C^∩Y)₂] (HC^∩Y = N,N-dimethylbenzylamine (C₆H₅CH₂NMe₂), N,N-dimethylnaphthylamine (C₁₀H₇NMe₂), tri-o-tolylphosphine {P(tol-o)₃}; ER=SePh, SeMes, TePh, TeMes (Mes = 2,4,6-Me₃C₆H₂). Similar reactions of [Pd₂(μ-Cl)₂(C₁₀H₆NMe₂-C,N)₂] with Pb(SMes)₂ or MesSH in the presence of NaHCO₃ gave chloro/thiolato-bridged complex [Pd₂(μ-Cl)(μ-SMes)(C₁₀H₆NMe₂-C,N)₂]. The newly synthesized complexes were characterized by elemental analysis, UV-Vis, IR, NMR (¹H, ¹³C, ³¹P, ⁷⁷Se, ¹²⁵Te) spectroscopy. These complexes crystallized out preferentially in sym-cis configuration. A low energy charge transfer transition has been identified from chalcogenolate centers to an emptyπ^* orbital of cyclometallated ligand in absorption spectroscopy in these complexes. The structures of [Pd₂(μ-Cl)(μ-SMes)(C₁₀H₆NMe₂-C,N)₂] (1) and [Pd₂(μ-SePh)₂(C₁₀H₆NMe₂-C,N) ₂] (3) have been established by single crystal X-ray diffraction analyses. In the former, the two palladium atoms are held together by chloro and thiolato bridges whereas in the latter, the two phenylselenolato ligands bridge two palladium atoms. The pyrolysis of [Pd(μ-TeMes)(C₁₀H₆NMe₂-C,N)]₂ (10) in a furnace gave Pd₇Te₃ whereas thermolysis in TOPO afforded primarily PdTe₂.

Full text of DOI:10.1016/j.ica.2008.01.005

Available online at www.sciencedirect.com
Inorganica Chimica Acta 361 (2008) 2462–2470
www.elsevier.com/locate/ica
Chalcogenolato-bridged cyclometallated binuclear palladium
complexes: Synthesis, spectroscopy, structures of
[Pd2(l-Cl)(l-SMes)(C10H6NMe2–C,N)2] and
[Pd2(l-SePh)2(C10H6NMe2–C,N)2]
a
a,
a,
b
*
*
Ninad D. Ghavale , Sandip Dey , Vimal K. Jain , M. Nethaji
a Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400 085, India
b Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore 560 012, India
Received 27 September 2007; received in revised form 8 January 2008; accepted 11 January 2008
Available online 19 January 2008
Abstract
Reactions of orthometallated binuclear palladium complexes with NaER, obtained by NaBH4 reduction of R2E2 in methanol, gave
complexes, [Pd2(l-ER)2(C\Y)2] (HC\Y = N,N-dimethylbenzylamine (C6H5CH2NMe2), N,N-dimethylnaphthylamine (C10H7NMe2),
tri-o-tolylphosphine {P(tol-o)3}; ER=SePh, SeMes, TePh, TeMes (Mes = 2,4,6-Me3C6H2). Similar reactions of [Pd2(l-Cl)2-
(C10H6NMe2–C,N)2] with Pb(SMes)2 or MesSH in the presence of NaHCO3 gave chloro/thiolato-bridged complex [Pd2(l-Cl)-
(l-SMes)(C10H6NMe2–C,N)2]. The newly synthesized complexes were characterized by elemental analysis, UV–Vis, IR, NMR (1H,
13C, 31P, 77Se, 125Te) spectroscopy. These complexes crystallized out preferentially in sym-cis configuration. A low energy charge transfer
transition has been identified from chalcogenolate centers to an empty p* orbital of cyclometallated ligand in absorption spectroscopy in
these complexes. The structures of [Pd2(l-Cl)(l-SMes)(C10H6NMe2–C,N)2] (1) and [Pd2(l-SePh)2(C10H6NMe2–C,N) ] (3) have been
2
established by single crystal X-ray diffraction analyses. In the former, the two palladium atoms are held together by chloro and thiolato
bridges whereas in the latter, the two phenylselenolato ligands bridge two palladium atoms. The pyrolysis of [Pd(l-TeMes)(C10H6NMe2–
C,N)]2 (10) in a furnace gave Pd7Te3 whereas thermolysis in TOPO afforded primarily PdTe2.
Ó 2008 Elsevier B.V. All rights reserved.
Keywords: Palladium; Orthometallation; Organochalcogenolates; Structures; NMR
1. Introduction
involving metal–carbon bond, and (iii) substitution of the
bridging ligands, have been reported for chloro/acetato-
bridged palladium complexes. The latter reaction has been
exploited to generate numerous mono- and bi-nuclear
derivatives. The nature of incoming anionic ligand governs
the overall nuclearity and stereochemistry of the complexes.
Thus bidentate anionic ligands (L–L) such as acacꢀ,
ðROÞ PSꢀ; and R2NCSꢀ yield mononuclear complexes
Cyclometallated palladium complexes have been investi-
gated extensively [1] since the early study by Cope and Siek-
man [2]. There are several obvious reasons for this sustained
interest in these complexes. These include their outstanding
applications in organic synthesis [3], metallomesogenic as
well as intriguing photophysical properties [4,5] and rich
reaction chemistry [1]. Three general reactions, viz.: (i)
bridge cleavage by neutral donor ligands, (ii) reactions
2
2
2
with chelating L–L [1,6], whereas small bite anionic ligands,
like 2-pySꢀ, afford binuclear complexes e.g., [Pd2(l-
Spy)2(C\N)2] (C\N = C6H4CH2NMe2) [7]. However, with
simple thiolate ligands, only mono-substituted derivatives
[Pd2(l-SR)(l-X)(C\N)2] (R = n-alkyl, But, Ph, p-tol;
X = Cl, OAc, O2CCF3; C\N = RC6H3CH@NC6H4R0,
*
Corresponding authors. Tel.: +91 22 25592589.
E-mail addresses: dsandip@barc.gov.in (S. Dey), jainvk@barc.gov.in
(V.K. Jain).
0020-1693/$ - see front matter Ó 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2008.01.005

N.D. Ghavale et al. / Inorganica Chimica Acta 361 (2008) 2462–2470
2463
and X-ray structural analysis. Treatment of [Pd2(l-
X)2(C\Y)2] with NaER in benzene–methanol mixture
afforded yellow to orange-red bis(organochalcogenolato)-
bridged complexes, [Pd2(l-ER)2(C\Y)2] (ER = SePh,
SeMes, TePh or TeMes) (Scheme 2). It is surprising that
the thiolato ligands afford mono-thiolato bridged com-
plexes, as reported earlier [8–10] and also observed during
this investigation, while the heavier chalcogenolate conve-
niently yields bis-RE (E = Se or Te) bridged derivatives.
This difference in reactivity may be attributed either to
higher nucleophilicity and higher donation ability of
SeR/TeR ligands than the RSꢀ group or relative size of
the chalcogen atoms. The effect of the latter is reflected in
NMe2
NMe2
Y
C
P(tol-o)2
=
,
,
CH2
(-C6H4CH2NMe2)
((o-tol)2PC6H4CH2-)
(-C10H6NMe2)
Scheme 1.
CH2C9H6N) [8–10], rather than the disubstituted com-
plexes, [Pd2(l-SR)2(C\N)2], could be isolated. This is in
contrast to the fact that both classical and organometallic
complexes, [Pd2X2(l-ER0)2(PR3)2] (X = Cl, Me; E = S or
Se), can be prepared conveniently in high yields [11–13].
Thus, we have examined the reactions of orthopalladated
compounds derived from nitrogen and phosphorus ligands
(Scheme 1) with organochalcogenolate ions (REꢀ; E = S,
Se, Te) in the hope of isolating bis(organochalcogenolate)-
bridged complexes. The heavier chalcogens (E = Se or Te)
did afford ‘‘Pd2(l-ER)2” bridged complexes. The results
of this work are reported herein.
˚
˚
Pdꢁ ꢁ ꢁPd separation, which is 3.46 A for 1 and 3.61 A for
3. The longer Pdꢁ ꢁ ꢁPd separation in 3 possibly helps in
reducing interatomic repulsion among organo groups
attached to chalcogen atom and metallated ligand. The sta-
bility of M–E bond in several transition metal complexes
increased in the order Te ꢂ Se > S [14].
The complexes containing metallated nitrogen ligand
were formed exclusively in sym-cis configuration. Accord-
2. Results and discussion
1
ingly in H NMR spectra (Table 1), two separate reso-
nances for EMes protons are observed. The 2,6-methyl
signals appeared either as two closely spaced singlets or
slightly broadened singlet. Similarly 77Se{1H} NMR spec-
trum of 3 exhibited two separate signals at d ꢀ10.7 and
ꢀ193.3 ppm; the former is assigned to SePh group trans
to nitrogen while the latter trans to the metallated carbon
atom of dimethylbenzylamine.
2.1. Synthesis and NMR spectroscopy
The reaction of [Pd2(l-Cl)2(C10H6NMe2–C,N)2] either
with Pb(SMes)2 or MesSH (Mes = 2,4,6-Me3C6H2) in the
presence of sodium bicarbonate gave a single molecular
species, which was characterized as sym-cis-[Pd2(l-Cl)(l-
SMes)(C10H6NMe2–C,N)2] (1) by microanalysis, NMR
N
C
N
C
Cl
Pb(SMes)2
Pd
Pd
S
Mes
1 (N∩C = C10H6NMe2)
R
MesSH + NaHCO3
Y
C
E
Y
Y
C
X
X
Y
C
2 NaER
Y∩C
Pd
Pd
Pd
Pd
C
E
R
ER
C6H4CH2NMe2
C10H6NMe2
SePh
SePh
SePh
2
3
4
5
6
7
8
9
(o-tol)2PC6H4CH2
C6H4CH2NMe2
C10H6NMe2
SeMes
SeMes
SeMes
TePh
(o-tol)2PC6H4CH2
C10H6NMe2
(o-tol)2PC6H4CH2
C10H6NMe2
TePh
TeMes 10
TeMes 11
(o-tol)2PC6H4CH2
Scheme 2.

Table 1
Electronic and NMR spectral data for organochalcogenolato-bridged orthometalled palladium(II) complexes
Complex
NMR d in ppm
UV–Visa
1H
13C{1H}
[Pd2(l-Cl)2(C6H4CH2NMe2–C,N)2]
[Pd2(l-Cl)2(C10H6NMe2–C,N)2]
2.79, 2.86 (NMe2); 3.93 (NCH2); 6.85–7.18 (m, 52.7 (NMe2); 73.4 (CH2–); 121.4; 124.7; 125.1; 133.2; 142.9 (C-2); 146.9 (C–Pd)
C6H4)
340
3.45, 3.49 (NMe2); 7.17–7.25 (m); 7.31–7.41
(m); 7.51 (d, 8 Hz); 7.61 (d, 8 Hz)
1.95 (s, MeCOO); 2.60 (br, tol); 6.81–7.23 (m,
tol)
54.4, 54.8 (each s, NMe2); 115.2; 123.2; 125.3; 126.2; 127.4; 129.0; 129.5; 134.8;
140.7; 155.4
301; 316; 327
[Pd2(l-OAc)2(P-tol2C6H4CH2–
C,P)2]b
sym-cis-[Pd2(l-Cl)(l-
SMes)(C10H6NMe2–C,N)2] (1)
22.2 (tol-Me); 24.1 (OAc); 30.2 (CH2Pd); 125.1; 127.3 (d, 25 Hz quart C); 130 (d, 357
53 Hz quart C); 142.0; 157.2 (d, 32 Hz, quart C), 180.1 (br, C@O)
21.0 (s, Me-4, MesS); 26.3 (s, Me-2,6, MesS); 52.6 (s, NMe2); 115.5; 122.7; 124.9;
126.2; 127.3; 128.4 (C-3,5 MesS); 129.5; 130.3; 132.9 (C-1 MesS); 134.7; 136.8;
141.2 (C-4, MesS); 142.8; 143.8 (C-2,6/MesS); 154.9
2.21 (s, SMes, Me-4); 3.30 (s, SMes, Me-2,6);
3.38 (s, NMe2); 6.67 (d, 7.3 Hz, 2H); 6.93 (s,
SMes+napthyl, 4H); 7.30–7.38 (m, 6H); 7.55
(d, 2.5 Hz, 2H)
sym-cis-[Pd2(l-
SePh)2(C6H4CH2NMe2–C,N)2]
(2)
2.50, 2.76 (s, NMe2); 3.91 (s, CH2–); 6.88–8.23 50.8 (s, NMe2); 72.2 (NCH2–); 122.0; 124.1; 125.8; 126.4; 127.8; 128.2; 135.5;
(m, Ph+C6H4) 135.9; 137.8; 145.4; 148.0 (Pd–C); 153.2
sym-cis-[Pd2(l-
3.28 (br, NMe2); 6.96–7.16 (m, 6H); 7.32–7.49 52.9 (s, NMe2); 115.3; 123.0; 124.8; 125.2; 126.1; 127.2; 130.9; 132.9; 141.5; 156.4. 306 (30050); 318 (29920); 328
SePh)2(C10H6NMe2–C,N)2] (3)c
(m, 6H); 7.62–7.76 (m, 4H); 8.01–8.18 (m, 2H); 125.9; 126.8; 128.2; 131.6; 132.0; 132.3; 136.3; 150.8 (due to SePh)
8.21–8.35 (m, 4H)
(29410)
sym-cis-[Pd2(l-SePh)2{P(o-
tol)2C6H4CH2–C,P}2] (4)d
2.47 (cis), 2.60 (trans) (each s, 2:1, tol-Me); 3.18 23.5 (s, tol-Me); 33.2 (trans), 34.5 (cis) (each s, 1:2 ratio, tol-CH2–); 124.8, 125.6, 283 (39890); 300 (35000); 360
(cis), 3.41 (trans) (each s, tol-CH2, 2:1);
127.2, 127.6,
6.81–7.44 (m, Ph+C6H4); 7.79 (d, 6.5 Hz)
127.8, 128.1, 129.5, 124.8–136.8 (peaks due to SePh+p-tol group) 142.1 (d,
11 Hz); 159.1 (d, 36 Hz, trans, PCH2–); 159.3 (d, 35 Hz, cis, PCH2–)
(19980)
[Pd2(l-SeMes)2(C6H4CH2NMe2–
C,N)2] (5)
2.24 (SeMes, 4-Me); 2.40 (NMe2); 3.17 (SeMes, 20.8 (SeMes, 4-Me); 27.4, 28.1, 28.3 (SeMes, 2,6-Me); 50.9, 51.4 (each s, NMe2); 272 (41700); 322 (sh, 20805);
2,6-Me); 3.74 (CH2N); 6.64 (br); 6.81–6.87 (m); 72.3 (s, CH2N); 121.4; 121.6; 123.8; 125.1; 128.4; 128.6; 128.7; 129.3; 129.9; 131.0; 395 (10940)
7.36–7.39 (m)
133.2; 134.2; 134.8; 135.5; 142.3; 142.6; 143.0; 147.8; 148.0; 152.7
[Pd2(l-SeMes)2(C10H6NMe2–
C,N)2] (6)
2.18, 2.22 (SeMes, 4-Me); 3.04, 3.07 (SeMes,
2,6-Me); 3.15; 3.23; 3.39; 6.89 (s, CH, 3,5 Mes); 114.7; 122.3; 124.3; 126.2; 126.9; 128.1; 128.5; 134.5; 135.2; 135.6; 141.2; 142.5;
20.6 (SeMes, 4-Me); 27.6; 28.0; 28.4 (SeMes, 2,6-Me); 52.5, 53.1 (each s, NMe2); 258 (sh, 37245); 307 (36870);
318 (37310); 328 (36750)
6.98–7.52 (m)
150.5; 156.0
[Pd2(l-SeMes)2{P(tol-
o)2C6H4CH2–C,P}2] (7)e
[Pd2(l-TePh)2(C10H6NMe2–C,N)2]
(8)
2.02; 2.22; 2.29; 2.34; 2.35; 2.39; 2.54; 2.91;
6.50–7.31 (m)
3.35, 3.40 (NMe2); 6.83–6.94 (m, 4H); 7.06–
7.15 (m, 3H); 7.31–7.39 (m, 6H); 7.59–7.69 (m, 135.7; 137.7; 140.2; 142.3; 144.1; 155.1; 156.2
4H); 7.94–8.00 (m, 2H); 8.18 (d, 7.6 Hz, 1H);
20.7 (SeMes, 4-Me); 23.1 (tol-Me); 26.3, 27.4 (SeMes, 2,6-Me cis); 33.1 (PCH2);
35.0; 124.5–136.4; 142.6; 143.6; 159.4 (d, 34 Hz, p-CH2).
52.1 (s, NMe2); 115.8; 123.0; 123.3; 124.8; 126.4; 127.1; 127.5; 128.4; 129.4; 135.4; 271 (sh, 28290); 307 (28330);
280 (sh, 50625); 319 (62825);
338 (sh, 49125); 372 (32875)
317 (27820); 327 (26155); 390
(14400)
8.36–8.40 (m, 2H)
[Pd2(l-TePh)2{P(tol-o)2C6H4CH2–
C,P}2] (9)f
2.39 (cis), 2.47 trans (2:1, tol-Me); 3.27 (cis),
3.49 (trans) (2:1, PCH2); 6.70–7.50 (m); 7.75 (d, due to TePh+p-tol carbons); 159.9 (d), 160.2 (d)
24.1 (s, tol-Me); 30.4 (trans), 31.7 (cis) (PCH2); 109.9 (Te–C); 124.6–142.0 (peaks 328 (23595); 387 (17410); 441
(13558)
7 Hz)
[Pd2(l-MesTe)2(C10H6NMe2–
C,N)2] (10)
2.19, 2.22 (s, 4-Me, Mes); 2.18–3.35
(NMe2+2,6-Me; Mes); 6.75–6.97, 7.37–7.83
(m, C10H6)
290 (42950); 305 (44310); 317
(42470); 327 (41558); 427
(16037)
1.97 (s, 4-Me, Mes); 2.18, 2.22, 2.27, 2.31 (each
s, 2,6-Me, Mes); 2.35 (s, tol-Me); 2.78 (s, tol-
CH2); 6.52, 6.62 (each s, CH, Mes); 6.87–7.07,
7.36 (m, tol-)
[Pd2(l-MesTe)2(P(o-
257 (79944); 322 (52519); 377
(31556)
tol)2C6H4CH2–C,P)2] (11)g
a
Wavelengths kmax at the absorption maxima in nm, molar extinction coefficients e in Mꢀ1 cmꢀ1
31P{1H} NMR (CDCl3): 36.5 (s, br). IR: 1576 cmꢀ1 (mCO).
.
b
c
d
e
f
77Se{1H} NMR (CDCl3) d ꢀ10.7, ꢀ193.3 ppm.
31P{1H} NMR (CDCl3): 34.9 (cis), 35.7 (trans); 77Se{1H} NMR (CDCl3) d: 77.1 (t, 130 Hz), ꢀ220 (s, ppm).
31P{1H} NMR (CDCl3): 32.8 (cis); 34.6 (trans isomer).
31P{1H} NMR (CDCl3): 32.9 (cis); 34.1 (trans).
31P{1H} NMR (CDCl3): 26.9 (cis); 39.5 (trans).
g

N.D. Ghavale et al. / Inorganica Chimica Acta 361 (2008) 2462–2470
2465
ε × 10−4 [M−1cm−1]
Unlike bis(chalcogenolate) complexes derived from met-
allated nitrogen ligands, the metallated o-tolylphosphine
derivatives were formed as a mixture of cis and trans iso-
mers with the predominance of the former. Accordingly,
these complexes displayed two resonances in their 31P
NMR spectra. From the spectral integration it can be
inferred that the trans isomer exists in 5–15% concentra-
tion. The 77Se{1H} NMR spectrum of 4 (Fig. 1) exhibited
two sets of resonances attributable to cis configuration.
The high frequency resonance appeared as a triplet due
to coupling with two equivalent trans phosphine ligands
(2J(77Se–31P) = 130 Hz). The low frequency resonance,
however, appeared as a singlet. The magnitude of cis
2J(77Se–31P) couplings is usually smaller than 10 Hz. The
observed coupling constants are in conformity with the val-
ues reported for mono- and bi- nuclear palladium/platinum
selenolate complexes [15,16]. The 77Se NMR resonance,
expected to appear as a doublet due to 2J(Se–P) couplings,
for the trans isomer could not be identified with confidence
owing to the low concentration (ꢃ5% by 31P NMR integra-
tion) of this isomer in solution. The formation of trans iso-
mer with metallated phosphine may be due to comparable
trans influence of P and E ligating atoms, as a consequence,
thermodynamic stability of cis and trans isomers may not
be significantly different.
8
6
4
2
0
250
300
350
400
λ /nm
450
500
550
600
Fig. 2. UV–Vis spectrum of [Pd2(l-TeMes)2(C10H6NMe2–C,N)2] (10) in
CH2Cl2 solution.
and 427 nm (Fig. 2). This long wavelength band at
kmax P 360 nm is tentatively assigned as charge transfer
transition from the selenolato/tellurolato centers of chalco-
genolate ligand to an empty p* orbital of the cyclometallat-
ed ligand (LLCT).
2.2. UV–Vis absorption spectroscopy
For these binuclear palladium complexes of d8 system, a
dr* ? p* metal-metal-to-ligand-charge-transfer (MMLCT)
is not preferred due to the absence of ground state metal–
All cyclometallated complexes have strong absorption
bands (e = 104 Mꢀ1 cmꢀ1) in the visible region in dichloro-
methane (Table 1). The observed transition at
kmax 6 360 nm may be assigned to the ligand-centered
(LC) charge transfer transition of the cyclometallated
ligand and dr*(Pd) ? p*(C\Y) metal-to-ligand-charge-
transfer (MLCT) transition [17,18]. All the bis(chalcogeno-
lato)-bridged complexes exhibited one band between 360
˚
metal interaction. The Pdꢁ ꢁ ꢁPd distance of 3.61 A for 3 is
too long to favor any inter-metal communication [17]. Also
no ligand-field d–d transition is expected in the observed
spectral region. The two strong ligands, viz., cyclometallat-
ed and heavier chalcogen, can cause only very weak but
high energy ligand-field d–d transitions appearing below
360 nm [18].
The tellurolato-bridged complexes have their absorption
band at lower energies at about 427 nm (10) as compared
to about 395 nm (5) for the Se complexes. In chemical
terms, the replacement of Se by stronger r donor Te desta-
bilizes the HOMO causing the bathochromic shift [19,20].
A hypsochromic shift of about 50 nm wavelength absorp-
tion is also observed in case of phosphine complexes. This
may be rationalized by the stronger back bonding interac-
tion between PdII and the phosphine acceptor destabilizing
the LUMO (p*), which is responsible for the blue shift. In
the analogous Pd/Te/naphthylamine complexes, the
increasing donor strength of mesityl group due to three
methyl groups in benzene ring is reflected in red shift of
kmax when compared between complexes 8 (390 nm) and
10 (427 nm). This long wavelength band for Pd/Se/naph-
thylamine complexes could not be marked. This may be
presumably due to blue shifting of the absorption as com-
pared to corresponding Te analogues, which are masked in
the tailing of highly intense typical three bands at ꢃ306,
318 and 328 nm of naphthylamine complexes of Pd(II).
ppm
100
0
-100
-200
Fig. 1. 77Se{1H} NMR spectrum of [Pd2(l-SePh)2(P(o-tol)2C6H4CH2–
C,P)2] (4).

2466
N.D. Ghavale et al. / Inorganica Chimica Acta 361 (2008) 2462–2470
Table 2
Selected bond lengths (A) and angles (°) for [Pd2(l-Cl)(l-
SMes)(C10H6NMe2–C,N)2] (1)
2.3. Crystallography
˚
The molecular structures of [Pd2(l-Cl)(l-SMes)(C10H6-
NMe2–C,N)2] (1) and [Pd2(l-SePh)2(C10H6NMe2–C,N)2]
(3) were established by single crystal X-ray diffraction
analyses. The ORTEP [21] drawings with atomic number-
ing scheme are shown in Figs. 3 and 4, and the selected
bond lengths and angles are given in Tables 2 and 3,
respectively.
Pd(1)–C(9)
Pd(1)–N(1)
Pd(1)–S(1)
Pd(1)–Cl(1)
C(1)–N(1)
S(1)–C(25)
1.982(7)
Pd(2)–C(21)
Pd(2)–N(2)
Pd(2)–S(1)
Pd(2)–Cl(1)
C(13)–N(2)
C(26)–C(31)
1.982(8)
2.136(7)
2.307(2)
2.469(2)
1.483(10)
1.497(10)
2.128(6)
2.303(2)
2.485(2)
1.474(10)
1.802(7)
C(9)–Pd(1)–N(1)
C(9)–Pd(1)–S(1)
C(9)–Pd(1)–Cl(1)
N(1)–Pd(1)–Cl(1)
N(1)–Pd(1)–S(1)
S(1)–Pd(1)–Cl(1)
Pd(1)–S(1)–C(25)
Pd(1)–N(1)–C(1)
Pd(1)–S(1)–Pd(2)
83.4(3)
96.5(2)
C(21)–Pd(2)–N(2)
C(21)–Pd(2)–S(1)
C(21)–Pd(2)–Cl(1)
N(2)–Pd(2)–Cl(1)
N(2)–Pd(2)–S(1)
S(1)–Pd(2)–Cl(1)
Pd(2)–S(1)–C(25)
Pd(2)–N(2)–C(13)
Pd(1)–Cl(1)–Pd(2)
84.1(3)
95.2(2)
Complex 1 has a sym-cis configuration with the nitrogen
atoms trans to the bridging thiolato ligand. A similar
configuration has been reported for [Pd2(l-Cl)(l-SBun)-
{(BunO)C6H3CH@NC6H4(OBun-4)}2] [9], ½Pd2ðl ꢀ OAcÞ
173.5(2)
93.52(17)
178.03(18)
86.79(7)
109.3(2)
108.9(5)
97.29(7)
177.3(2)
93.57(19)
178.83(19)
87.10(7)
108.3(2)
108.2(5)
88.63(7)
ðl ꢀ SBunÞfðBunNÞC6H3CH@NC6H4NO2 ꢀ 4g2ꢄ [10] and
2
[Pd2(l-O2CCF3)(l-SBut)(
)2] [8]. The two palla-
N
dium–carbon distances are similar and are well in agree-
ment to those found in cyclopalladated amine complexes
[6,10]. The two Pd–S bond lengths are comparable and
are within the range reported for bridging thiolato com-
plexes [22,23]. The Pd–N distances are slightly shorter than
the mixed carboxylato–thiolato bridged derivatives [Pd2(l-
O2CR)(l-SR0)(C\N)2] [8,10], but are similar to the one
observed for [Pd2(l-Cl)(l-SBun){(BunO)C6H3CH@NC6H4-
(OBun-4)}2] [9].
The metallated N,N0-dimethylnapthylamine forms a pla-
nar five-membered N\C chelate ring with bite angle of
ꢃ84°, which can be compared with the angle reported for
Fig. 3. Molecular structure of [Pd2(l-Cl)(l-SMes)(C10H6NMe2–C,N)2]
(1). H atoms were omitted for clarity.
Fig. 4. Molecular structure of [Pd2(l-SePh)2(C10H6NMe2–C,N)2] (3). H atoms were omitted for clarity.

N.D. Ghavale et al. / Inorganica Chimica Acta 361 (2008) 2462–2470
2467
Table 3
as inferred from the calculated weight loss and XRD pat-
tern [35]. To prepare large quantities of the telluride, a sub-
stantial amount (100–200 mg) of complex 10 was heated in
a furnace at 465 °C for 2 h under a dynamic dry argon
atmosphere. The weight loss, XRD pattern and EDAX
(Anal. Calc. for Pd7Te3: Pd, 66.1; Te, 33.9. Found: Pd,
62.6; Te, 37.4%) of the residue matched well with Pd7Te3
[35] as obtained from TG. To identify the intermediate
product formed at 265 °C in TG, we have pyrolysed 10
in a preheated furnace at 265 °C for 2 h. The XRD pattern
of this residue indicates the formation of a mixture of pal-
ladium tellurides, mainly Pd9Te4 and Pd2Te. Pyrolysis of
10 in refluxing (202 °C) tri-n-octylphosphine oxide for 6 h
gave a black residue, which has been identified as PdTe2
from XRD pattern (supplementary material) [36]. Evi-
dently depending on pyrolysis temperature, different palla-
dium tellurides are formed seemingly by tellurium
elimination on increasing temperature. Palladium is known
to form several tellurides differing in stoichiometry and
structures [37].
˚
Selected bond lengths (A) and angles (°) for [Pd2(l-SePh)2(C10H6NMe2–
C,N)2] (3)
Pd(1)–C(1)
Pd(1)–N(1)
Pd(1)–Se(1)
Pd(1)–Se(2)
Se(1)–C(31)
N(1)–C(9)
2.009(5)
2.153(4)
2.5522(7)
2.3881(7)
1.937(5)
1.478(7)
Pd(2)–C(13)
Pd(2)–N(2)
Pd(2)–Se(1)
Pd(2)–Se(2)
Se(2)–C(25)
N(2)–C(21)
1.991(5)
2.151(4)
2.5543(7)
2.3874(7)
1.936(5)
1.466(7)
N(1)–Pd(1)–Se(1)
C(1)–Pd(1)–Se(2)
C(1)–Pd(1)–Se(1)
N(1)–Pd(1)–C(1)
Se(1)–Pd(1)–Se(2)
Se(2)–Pd(2)–N(2)
Pd(1)–Se(1)–Pd(2)
Pd(1)–Se(1)–C(31)
Pd(2)–Se(1)–C(31)
98.18(11)
94.22(16)
177.69(15)
83.10(19)
84.62(2)
176.97(11)
89.94(2)
99.23(15)
100.64(15)
N(2)–Pd(2)–Se(1)
C(13)–Pd(2)–Se(2)
Se(1)–Pd(2)–C(13)
N(2)–Pd(2)–C(13)
Se(1)–Pd(2)–Se(2)
Pd(1)–Se(2)–Pd(2)
Pd(1)–Se(2)–C(25)
Pd(2)–Se(2)–C(25)
98.21(12)
94.02(16)
178.60(16)
83.2(2)
84.59(2)
98.18(2)
102.51(16)
102.35(15)
cyclometallated amine ligands [8–10]. The chelated metal-
lated rings and four-membered Pd2SCl ring are co-planar.
The S–Pd–Cl angles are significantly smaller than the ideal
value (90°) indicating strain in the four-membered ring.
Consequently, S–Pd–C and Cl–Pd–N angles have opened
up. The Pd–S–Pd angle is within the range reported for
thiolato-bridged complexes (79–102°) [8–10,24].
Complex 3 consists of two distorted square planar palla-
dium atoms, which are held together by two phenylseleno-
lato bridges. The phenyl groups of the PhSe ligand adopt
an anti configuration. The molecule has a sym-cis configu-
ration with a non-planar four-membered Pd2Se2 ring, as
observed in [Pt2Cl2(l-SeBz)2(PPr3)2] [25]. However, in
other selenolato-bridged phosphine derivatives, [M2Cl2(l-
SeR0)2(PR3)2] (M/R0/R = Pd/CH2CH2COOMe/Ph [26],
Pt/Et/Et [27]), the four-membered M2Se2 ring is planar.
The five membered metallated amine is in plane with the
coordination plane of the palladium.
3. Conclusions
Binuclear cyclometallated palladium complexes contain-
ing bis-selenolato/tellurolato bridge have been synthesized
conveniently. The cis and trans isomerism has been
observed for cyclometallated phosphine derivatives with
the predominance of the former, on the other hand cyclo-
metallated heterocyclic nitrogen ligands afford the cis iso-
mer exclusively. A charge transfer transition has been
observed from chalcogen center to an empty p* orbital of
the cyclometallated ligand. The tellurolato derivatives have
been demonstrated to serve as molecular precursors for the
preparation of palladium tellurides.
4. Experimental
There are two distinct Pd–Se bonds (Table 3). The bond
˚
trans to carbon is longer (ꢃ0.17 A) than the one trans to
4.1. General
nitrogen reflecting strong trans influence of the metallated
carbon. These distances can be compared with those
reported for [M2Cl2(l-SeR0)2(PPr3)2] [25–27] and other
Elemental analysis were carried out on a Carlo-Erba
EA-1110 CHN-O instrument. Melting points were deter-
mined in capillary tubes and are uncorrected. 1H,
13C{1H}, 31P{1H}, 77Se{1H} and 125Te{1H} NMR spectra
were recorded on a Bruker DPX-300 NMR spectrometer
operating at 300, 75.47, 121.5, 57.24 and 94.86 MHz,
respectively. Chemical shifts are relative to internal chloro-
˚
related derivatives [28–31]. The Pd–N distances (2.15 A)
are slightly longer than those reported in [Pd2Cl2(l-
Me2pz)2(PMe2Ph)2] (Pd–N = 2.03–2.08 A) [32], [Pd3(l-
pz)6] (Pd–Nav = 2.00 A) [33], but are closer to mononuclear
˚
˚
˚
complex [PdCl(SeCH2CH2NMe2)(PPh3)] (Pd–N = 2.16 A)
1
form peak (d 7.26 H and 77.0 for 13C) and external 85%
[34]. The Pd–C distances are in good agreement with
reported values [6,24]. Various angles around palladium
atoms and in the four-membered Pd2Se2 ring of 3 are sim-
ilar to those observed for 1.
H3PO4 for 31P, external Me2Se for 77Se{1H} (secondary
reference Ph2Se2 in CDCl3, d 463 ppm) and [Te(dtc)2]
(d = 0 ppm;
dtc=N,N-diethyldithiocarbamate)
for
125Te{1H} NMR spectra. A 90° pulse was used in every
case. A weighting function was applied in 77Se{1H} and
125Te{1H} NMR spectra. Electronic spectra were recorded
on a Chemito Spectrascan UV 2600 spectrophotometer. IR
data were recorded on a Bomem MB-102 FT-IR spectro-
photometer. TG curves were obtained at a heating rate
of 10 °C minꢀ1 under flowing argon on a Nitzsch STA
2.4. Thermal studies
Thermogravimetric analysis of 10 was carried out under
a flowing argon atmosphere. The TG curve of 10 showed
two well separated steps of decomposition at 265 and
465 °C, respectively, leading to the formation of Pd7Te3

2468
N.D. Ghavale et al. / Inorganica Chimica Acta 361 (2008) 2462–2470
PC-Luxx TG-DTA instrument. EDAX were carried out
with a Tescan Vega 2300T/40 instrument. Powder XRD
patterns were recorded on a Philips PW1820 using Cu
Ka radiation.
Vis (CH2Cl2) kmax in nm: 290 (25250); 302 (22880);
316 (18875); 327 (15625); 350 (sh, 9550). 1H NMR
was consistent with the spectrum obtained for the sam-
ple prepared via route (a).
4.2. Materials
4.3.3. Di-l-phenylselenolatobis[o-(di-o-
Solvents were dried and distilled under a nitrogen atmo-
sphere prior to use according to literature method [38]. All
reactions were carried out in Schlenk flask under a nitrogen
atmosphere. N,N-dimethylbenzylamine, N,N-dimethyl-
naphthylamine, tri-o-tolylphosphine, MesBr (Mes = 2,4,6-
Me3C6H2), Ph2Se2 and other reagents were obtained from
commercial sources and were used without further purifica-
tion. Palladium precursors, [Pd(OAc)2]3 [39], Na2[PdCl4]
[40], [Pd(l-Cl)(Y\C)]2 (Y\CH @ N,N-dimethylbenzyl-
amine, N,N-dimethylnaphthylamine [41], tri-o-tolylphos-
phine [42]), Mes2S2 [43], Mes2Se2 [44], Mes2Te2 [45] and
Ph2Te2 [46] were prepared according to literature methods.
tolylphosphino)benzyl]dipalladium(II) (4)
To a benzene solution (10 cm3) of NaSePh (prepared by
NaBH4 (15 mg, 0.396 mmol), reduction of diphenyl disele-
nide (65 mg, 0.208 mmol) in methanol (3 cm3)), a solution
of
trans-di(l-acetato)-bis[o-(di-o-tolylphosphino)benzyl]
dipalladium(II) (195 mg, 0.207 mmol) in benzene (10 cm3)
was added and stirred for 4 h at room temperature. The
solvents were evaporated under vacuum and the residue
was washed with hexane and extracted with benzene. The
extract was passed through a Florisil column. The filtrate
was concentrated and few drops of hexane were added to
obtain a yellow solid (118 mg, 50%).
4.3. Preparations
4.3.4. Di-l-mesitylselenolatobis[(N,N-
dimethylbenzylamine-2C,N)]dipalladium(II) (5)
4.3.1. Bis(mesitylthiolato)lead(II)
To a benzene solution of NaSeMes (prepared by
NaBH4 (30 mg, 0.79 mmol), reduction of dimesityl disel-
enide (150 mg, 0.37 mmol) in methanol (3 cm3)), a solu-
tion of di-l-chlorobis(N,N-dimethylbenzylamine-2C,N)
dipalladium(II) (208 mg, 0.37 mmol) in benzene (10 cm3)
was added and stirred for 4 h at room temperature.
The solvents were evaporated under vacuum and residue
was washed with hexane and extracted with benzene. The
extract was passed through a Florisil column. The filtrate
was concentrated in vacuo and few drops of hexane were
added to obtain orange-red solid (98 mg, 30%). All other
bi-nuclear complexes were prepared in a similar manner.
Pertinent data are summarized in Table 4.
To a benzene solution of NaSMes [prepared by NaBH4
(388 mg, 10.2 mmol), reduction of dimesityl disulphide
(1.502 g, 4.9 mmol) in methanol], a solution of Pb(OAc)2
(1.882 g, 4.9 mmol) in methanol was added and stirred
for 4 h at room temperature whereupon a yellow-brown
precipitate formed, which was filtered and washed with
methanol, water, acetone and ether. The solid was dried
in vacuo (516 mg, 20%, m.p. 250 °C).
4.3.2. l-Chloro-l-mesitylthiolatobis[(N,N-
dimethylnapthylamine-2C,N)]dipalladium(II) (1)
(a) To a benzene solution of [Pd2(l-Cl)2(C10H6NMe2–
C,N)2] (242 mg, 0.38 mmol), Pb(SMes)2 (205 mg,
0.40 mmol) was added with stirring at room tempera-
ture. The solution turned brown after few minutes.
After stirring the solution for 4 h, the solvent was evap-
orated under vacuum and the residue was washed with
hexane and ether and then was extracted with benzene.
The extract was filtered and the filtrate was concen-
trated to 5 cm3 followed by the addition of hexane
(3 cm3) to precipitate a yellow solid, which was filtered
out and recrystallised from dichloromethane–acetone–
hexane (171 mg, 60%).
(b) To a methanol solution of 2,4,6-trimethylthiophenol
(52 mg, 0.34 mmol) containing NaHCO3 (30 mg, 0.40
mmol), a solution of di-l-chlorobis(N,N-dimethylnap-
thylamine-2C,N)dipalladium(II) (213 mg, 0.34 mmol)
in benzene was added and stirred at room temperature
for 4 h. The solvents were evaporated under vacuum
and residue was washed with hexane and then was
extracted with benzene. The extract was filtered and
the filtrate was concentrated and a few cm3 of hexane
was added to yield a yellow solid (50 mg, 40%). UV–
4.3.5. Di-l-mesityltellurolatobis[(N,N-
dimethylnapthylamine-2C,N)]dipalladium(II) (10)
A benzene (10 cm3) solution of di-l-chlorobis(N,N-dim-
ethylnapthylamine-2C,N)dipalladium(II) (195 mg, 0.31
mmol) was added to a freshly prepared methanolic solution
(10 cm3) of NaTeMes (prepared by the reduction of dimes-
ityl ditelluride (159 mg, 0.32 mmol) by methanolic NaBH4
(26 mg, 0.68 mmol)), and stirred for 4 h at room tempera-
ture. The solvents were evaporated under vacuum, the res-
idue was washed with hexane and extracted with benzene
(3 ꢅ 10 cm3). The extract was passed through a Florisil col-
umn. The volume of extract was reduced to 5 cm3, few
drops of hexane were added to yield (147 mg, 45%) a
brown-red solid. M.p.: 160 °C (dec.). UV–Vis (CH2Cl2)
kmax in nm: 290 (42950); 305 (44310); 317 (42470); 327
(41558); 427 (16037).
4.4. Crystallography
The unit cell parameters and the intensity data for a yel-
low single crystals of 1 and 3 were collected at 0 and 20 °C,

N.D. Ghavale et al. / Inorganica Chimica Acta 361 (2008) 2462–2470
2469
Table 4
Physical and analytical data of chalcogenolato-bridged orthometallated palladium(II) complexes
Complex
Recrystallisation solvent (yield%)
M.p. (°C)
% Analysis Found (Calc.)
C
H
N
[Pd2(l-Cl)(l-SMes)(C10H6NMe2–C, N)2] (1)a
[Pd2(l-SePh)2(C6H4CH2NMe2–C,N)2] (2)
[Pd2(l-SePh)2(C10H6NMe2–C,N)2] (3)
[Pd2(l-SePh)2(P(o-tol)2C6H4CH2–C,P)2] (4)
[Pd2(l-SeMes)2(C6H4CH2NMe2–C,N)2] (5)
[Pd2(l-SeMes)2(C10H6NMe2–C,N)2] (6)
[Pd2(l-SeMes)2(P(o-tol)2C6H4CH2–C,P)2] (7)
[Pd2(l-TePh)2(C10H6NMe2–C,N)2] (8)
dichloromethane–acetone–hexane (60)
benzene–hexane (40)
benzene–hexane (39)
benzene–hexane (50)
benzene–hexane (43)
benzene–hexane (55)
benzene–hexane (32)
benzene–hexane (34)
benzene–hexane (38)
benzene–hexane (45)
benzene–hexane (34)
237 (dec.)
155
153
121
170
217
222
129
135
54.2 (53.6)
46.0 (45.4)
49.4 (50.0)
57.3 (57.3)
50.0 (49.3)
52.5 (53.1)
58.7 (59.3)
45.3 (44.9)
51.8 (52.8)
48.0 (48.2)
54.4 (54.9)
5.0 (4.8)
4.2 (4.3)
3.8 (4.0)
4.3 (4.5)
5.5 (5.3)
4.8 (4.9)
5.0 (5.1)
3.4 (3.6)
3.7 (4.1)
4.3 (4.4)
4.7 (4.8)
4.1 (3.8)
3.7 (3.5)
3.4 (3.2)
3.5 (3.2)
3.4 (3.2)
2.8 (2.9)
3.0 (2.8)
[Pd2(l-TePh)2(P(o-tol)2C6H4CH2–C,P)2] (9)
[Pd2(l-TeMes)2(C10H6NMe2–C,N)2] (10)
[Pd2(l-TeMes)2(P(o-tol)2C6H4CH2–C,P)2] (11)
160 (dec)
210
a
S: 4.1 (4.3).
Table 5
Manchanda, Head, Radiochemistry Division, BARC for
providing microanalysis of the complexes.
Crystallographic and structure refinement details for [Pd2(l-Cl)(l-
SMes)(C10H6NMe2–C, N)2] (1) and [Pd2(l-SePh)2(C10H6NMe2–C,N)2] (3)
Chemical formula
C33H35ClN2Pd2S
C36H34N2Pd2Se2
Appendix A. Supplementary material
(1)
(3)
Formula weight
Crystal size (mm)
Crystal system
Space group
Unit cell dimensions
739.94
865.37
0.44 ꢅ 0.33 ꢅ 0.28 0.54 ꢅ 0.11 ꢅ 0.04
CCDC 651065 and 651066 contain the supplementary
crystallographic data for [Pd2(l-Cl)(l-SMes)(C10H6NMe2–
C,N)2] (1) and [Pd2(l-SePh)2(C10H6NMe2–C,N)2] (3). These
data can be obtained free of charge from The Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif. Supplementary data associated with this
article can be found, in the online version, at doi:10.1016/
j.ica.2008.01.005.
orthorhombic
Pbca
monoclinic
P21/c
˚
a (A)
12.699(3)
21.659(6)
22.424(6)
12.6917(14)
11.6796(12)
22.584(2)
95.040(2)
3334.8(6)
1.724
˚
b (A)
˚
c (A)
b (°)
3
˚
Volume (A )
6168(3)
1.594
Dcalc (g cmꢀ1
)
Z
8
4
l (mmꢀ1)/F(000)
1.345/2976
1.82–27.99
0.733
3.288/1696
1.81–27.70
0.988
References
h Range for data collection (°)
Goodness of fit on F2
Absorption correction
Reflections collected/unique
Data/restraints/parameters
Final R1, wR2 indices
SADABS
SADABS
[1] V.K. Jain, L. Jain, Coord. Chem. Rev. 249 (2005) 3075.
[2] A.C. Cope, R.W. Siekman, J. Am. Chem. Soc. 87 (1965) 3272.
[3] A.D. Ryabov, Synthesis (1985) 233.
[4] P. Espinet, M.A. Esteruelas, L.A. Oro, J.L. Serrano, E. Sola, Coord.
Chem. Rev. 117 (1992) 215.
[5] A.P. Polishchuk, T.V. Timofeeva, Russian Chem. Rev. 62 (1993) 291.
[6] S. Narayan, V.K. Jain, R.J. Butcher, J. Organomet. Chem. 549 (1997)
73.
68573/7410
7410/0/359
0.051, 0.124
0.121, 0.178
0.73
28384/7828
7828/0/383
0.048, 0.087
0.108, 0.106
0.99
R1, wR2 (all data)
Largest difference in peak and
ꢀ3
˚
hole (e A
)
[7] A.J. Deeming, M.N. Meah, P.A. Bates, M.B. Hursthouse, J. Chem.
Soc., Dalton Trans. (1988) 2193.
[8] J. Ruiz, N. Cutillas, J. Torregrosa, G. Garcia, G. Lopez, P.A.
Chaloner, P.B. Hitchcock, R.M. Harrison, J. Chem. Soc., Dalton
Trans. (1994) 2353.
[9] J. Buey, G.A. Diez, P. Espinet, S. Garcia-Granda, E. Perez-Carreno,
Eur. J. Inorg. Chem. (1998) 1235.
respectively, on a Bruker Smart Apex CCD diffractometer
using graphite monochromated Mo Ka radiation
˚
(k = 0.71073 A), employing the x–2h scan technique. The
intensity data were corrected for Lorentz, polarization
and absorption effects. The structure was solved using the
SHELXS97 [47] and refined using the SHELXL97 [48] computer
programs. The non-hydrogen atoms were refined
anisotropically. Selected crystallographic data are given
in Table 5.
[10] J. Buey, S. Coco, L. Diez, P. Espinet, J.M. Martin-Alvarez, J.A.
Miguel, S. Garcia-Granda, A. Tesouro, I. Ledoux, J. Zyss, Organo-
metallics 17 (1998) 1750.
[11] V.K. Jain, Inorg. Chim. Acta 133 (1987) 261.
[12] V.K. Jain, S. Kannan, J. Organomet. Chem. 439 (1992) 231.
[13] A. Singhal, V.K. Jain, J. Chem. Soc., Dalton Trans. (1993) 1515.
[14] W. Levason, G. Reid, in: J.A. McCleverty, T.J. Meyer (Eds.),
Comprehensive Coordination Chemistry, vol. 1, Pergamon, Oxford,
2004, p. 395.
Acknowledgments
[15] S. Dey, V.K. Jain, A. Knoedler, W. Kaim, S. Zalis, Eur. J. Inorg.
Chem. (2001) 2965.
We thank Drs. T. Mukherjee and D. Das for the encour-
agement of this work. We are grateful to Dr. V.K.
[16] S. Dey, L.B. Kumbhare, V.K. Jain, T. Schurr, W. Kaim, A. Klein, F.
Belaj, Eur. J. Inorg. Chem. (2004) 4510.

2470
N.D. Ghavale et al. / Inorganica Chimica Acta 361 (2008) 2462–2470
[17] S.-W. Lai, T.-C. Cheung, M.C.W. Chan, K.-K. Cheung, S.-M. Peng,
C.-M. Che, Inorg. Chem. 39 (2000) 255.
[34] S. Dey, V.K. Jain, S. Chaudhury, A. Knoedler, F. Lissner, W. Kaim,
J. Chem. Soc., Dalton Trans. (2001) 723.
[18] L. Chassot, A.V. Zelewsky, Inorg. Chem. 26 (1987) 2814.
[19] S. Dey, V.K. Jain, A. Knoedler, A. Klein, W. Kaim, S. Zalis, Inorg.
Chem. 41 (2002) 2864.
[20] S. Dey, V.K. Jain, J. Singh, V. Trehan, K.K. Bhasin, B. Varghese,
Eur. J. Inorg. Chem. (2003) 744.
[21] C.K. Johnson, ORTEP II-A FORTRAN Thermal Ellipsoid Plot
Program for Crystal Structure Illustrations, ORNL-5138, 1976.
[22] I. Schneider, M. Ho¨rner, R.N. Olendzki, J. Stra¨hle, Acta Cryst. C49
(1993) 2091.
[35] Powder diffraction File No. 43-1294, compiled by JPCDS, Interna-
tional Centre for Diffraction Data, USA, 1986.
[36] Powder diffraction File No. 29-0970, compiled by JPCDS, Interna-
tional Centre for Diffraction Data, USA, 1986.
[37] S. Dey, V.K. Jain, Platinum Met. Rev. 48 (2004) 16.
[38] D.D. Perrin, W.L.F. Armarego, D.R. Perrin, Purification of Labo-
ratory Chemicals, 2nd ed., Pergamon, Oxford, 1980.
[39] V.I. Bakhmutov, J.F. Berry, F.A. Cotton, S. Ibragimov, C.A.
Murillo, Dalton Trans. (2005) 1989.
[23] V.K. Jain, R.P. Patel, K.V. Muralidharan, R. Bohra, Polyhedron 8
(1989) 2151.
[40] F.R. Hartley, The Chemistry of Platinum and Palladium, Wiley, New
York, 1973.
[24] V.K. Jain, R.P. Patel, K. Venkatasubramanian, Polyhedron 10 (1991)
851.
[41] A.D. Ryabov, V.A. Polyakov, A.K. Yatsimirsky, J. Chem. Soc.,
Perkin Trans. II (1983) 1503.
¨
[25] S. Dey, V.K. Jain, B. Varghese, J. Organomet. Chem. 623 (2001) 48.
[26] L.B. Kumbhare, V.K. Jain, P.P. Phadnis, M. Nethaji, J. Organomet.
Chem. 692 (2007) 1546.
[42] W.A. Herrmann, C. Brossmer, K. Ofele, C.P. Reisinger, T. Prierme-
ier, M. Beller, H. Fischer, Angew. Chem., Int. Ed. Engl. 34 (1995)
1844.
[27] V.K. Jain, S. Kannan, R.J. Butcher, J.P. Jasinski, Polyhedron 14
(1995) 3641.
[43] A.J. Costanza, R.J. Coleman, R.M. Pierson, C.S. Marvel, C. King, J.
Poly. Sci. XVII (1955) 319.
[28] R. Oilunkaniemi, R.S. Laitinen, M. Ahlgren, J. Orgonomet. Chem.
623 (2001) 168.
[44] M. Bochmann, K.J. Webb, M.B. Hursthouse, M. Mazid, J. Chem.
Soc., Dalton Trans. (1991) 2317.
[29] L.B. Kumbhare, V.K. Jain, R. Butcher, Polyhedron 25 (2006) 3159.
[30] S. Dey, V.K. Jain, A. Klein, W. Kaim, Inorg. Chem. Commun. 7
(2004) 601.
[31] S. Dey, V.K. Jain, B. Varghese, T. Schurr, M. Niemeyer, W. Kaim,
R.J. Butcher, Inorg. Chim. Acta 359 (2006) 1449.
[32] V.K. Jain, S. Kannan, E.R.T. Tiekink, J. Chem. Soc., Dalton Trans.
(1992) 2231.
[45] M. Akiba, M.V. Lakshmikantham, K.-Y. Jen, M.P. Cava, J. Org.
Chem. 49 (1984) 4819.
[46] W.A. Herrmann, C.E. Zybill, in: W.A. Herrmann (Ed.), Synthetic
Methods of Organometallic Chemistry and Inorganic Chemistry, vol.
4, Georg Thieme Verlog, Stuttgart, 1997, p. 205.
[47] G.M. Sheldrick, SHELXS-97, Program for Crystal Structure Determi-
nation, Universita¨et Go¨ttingen, Go¨ttingen, Germany, 1997.
[48] G.M. Sheldrick, SHELXL-97, Program for Refinement of Crystal
Structures, Universita¨et Go¨ttingen, Go¨ttingen, Germany, 1997.
[33] K. Umakoshi, Y. Yamauchi, K. Nakamiya, T. Kojima, M. Yama-
saki, H. Kawano, M. Onishi, Inorg. Chem. 42 (2003) 3907.