Structural chemistry of dihalogenopalladium(II) and platinum(II) complexes of heteroleptic N,S- and N,Se-donor ligands based on the 2- organochalcogenomethylpyridine motif

Article abstract of DOI:10.1016/j.ica.2011.06.032

The structural chemistry of dihalogenopalladium(II) and platinum(II) complexes of 2-organochalcogenomethylpyridine ligands is described. Complexes with a methyl group in the 6-position of the pyridyl ring, 6-MepyCH ₂ER, form dimeric complexes [

Full text of DOI:10.1016/j.ica.2011.06.032

Inorganica Chimica Acta 376 (2011) 290–295
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Structural chemistry of dihalogenopalladium(II) and platinum(II) complexes
of heteroleptic N,S- and N,Se-donor ligands based on the
2-organochalcogenomethylpyridine motif
⇑
⇑
Roderick C. Jones , Allan J. Canty, Michael G. Gardiner , Vicki-Anne Tolhurst
School of Chemistry, University of Tasmania, Hobart, Tasmania 7001, Australia
a r t i c l e i n f o
a b s t r a c t
Article history:
The structural chemistry of dihalogenopalladium(II) and platinum(II) complexes of 2-organochalcogenom-
ethylpyridine ligands is described. Complexes with a methyl group in the 6-position of the pyridyl ring,
6-MepyCH2ER, form dimeric complexes [trans-PdX2(l-6-MepyCH2SePh-N,Se)]2 (X = Br (1), I (2)) or mono-
nuclear complexes trans-PdI2(6-MepyCH2SR-N)2 (R = Me (5), Ph (6)). Absence of a 6-methyl substituent
results in the bidentate configuration observed for PdI2(pyCH2SePh-N,Se) (3) and PdI2(4-MepyCH2SMe-
N,S) (4). Related platinum(II) complexes are mononuclear including PtCl2(6-MepyCH2SPh-N,S) (8) as an
Received 29 January 2011
Accepted 17 June 2011
Available online 30 June 2011
Keywords:
Palladium
Platinum
Nitrogen–sulfur ligands
Nitrogen–selenium ligands
Heteroleptic ligands
Pyridine ligands
analogue of trimeric [trans-PdCl2(
appear to result from a combination of steric and electronic factors.
Ó 2011 Elsevier B.V. All rights reserved.
l-6-MepyCH2SPh-N,S)]3. Differences between palladium and platinum
1. Introduction
at room temperature, followed by evaporation to low volume
and addition of diethyl ether. In the solid state the complexes have
the formulations shown in Eqs. (1)–(4) based on X-ray structural
studies. The complexes exhibit microanalyses consistent with for-
mulations revealed by X-ray structural analysis. LSIMS mass spec-
tra show [MꢀX]+ for the mononuclear complexes, while the dimers
exhibit breakdown to the monomer [½MꢀX]+. Complexes 5 and 6
are obtained in higher yield from reagents in 1:2 mole ratio, and
are also formed if the reaction stoichiometry is maintained at
1:1 mole ratio.
The bidentate heteroleptic ligand system based on the 2-organ-
ochalcogenomethylpyridine motif (I) is one of the most widely
employed N,S-donors for studies of coordination [1,2] and organo-
metallic chemistry of palladium [2,3], and applications in organic
synthesis and catalysis [4,5]. In recent characterization of dichloro-
palladium(II) complexes of this system, PdX2(I), for investigation as
pre-catalysts in Mizoroki–Heck [5a–c], Suzuki–Miyaura [5b] and
Sonogashira and related catalysis [5d,e], we noticed that ligands
containing R6 = Me give dimeric (II) and trimeric (III) species, rather
than mononuclear PdCl2(I-N,E) [5c]. To explore the structural effect
of R6 = Me further we have undertaken the synthesis and X-ray
crystallographic examination of selected complexes and represen-
tative dichloroplatinum(II) complexes. Complexes studied include
bromo- and iodo-donors in place of chloro- to assess the effect of
larger halogens, and typical complexes where a 6-methyl group is
not present (Scheme 1).
PdX2ðNCMeÞ2 þ 6-MepyCH2SePh ! 1=2½PdX2ðl-6-MepyCH2SePh-N;SeÞꢁ2
1 : X ¼ Br; 2 : X ¼ I
ð1Þ
PdI2ðNCMeÞ þ R4-pyCH ER ! PdI2ðR4-pyCH ER1-N; EÞ
ð2Þ
2
2
2
3 : R1 ¼ SePh; R4 ¼ H
4 : R1 ¼ SMe; R4 ¼ Me
PdI2ðNCMeÞ þ 6-MepyCH SR1 ! 1=2PdI2ð6-MepyCH SR1-NÞ
2
2
2
2
2. Results
5 : R1 ¼ Me; 6 : R1 ¼ Ph
ð3Þ
ð4Þ
Complexes were readily obtained in 78–97% yield from the
reaction of PdX2(X = Br, I) or PtCl2 with the ligand in acetonitrile
PtCl2ðNCMeÞ þ 6-MepyCH SR1 ! PtCl2ð6-MepyCH SR1-N; SÞ
2
2
2
7 : R1 ¼ Me; 8 : R1 ¼ Ph
⇑
Corresponding authors. Tel.: +61 3 6226 2404; fax: +61 3 6226 2858.
E-mail address: Michael.Gardiner@utas.edu.au (M.G. Gardiner).
0020-1693/$ - see front matter Ó 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2011.06.032

R.C. Jones et al. / Inorganica Chimica Acta 376 (2011) 290–295
291
Me
N
SPh
PdCl2
N
R4
N
SePh
PdCl2
Cl2Pd
PhS
Cl2Pd
PhSe
N
R6
ER1
N
Me
Pd
Cl2
S
N
Ph
I: R4,R6-pyCH2ER1
II: 6-MepyCH2SePh
III: 6-MepyCH2SPh
Scheme 1. I: R4,R6-pyCH2ER1. II: 6-MepyCH2SePh. III: 6-MepyCH2SPh.
The results of the single crystal X-ray studies are illustrated in
Scheme 2 and Figs. 1–3; selected bond distances and angles are
given in Tables 1–4. Complexes 4,5 and 7 have one molecule in
the asymmetric unit; 3 and 8 contain three and two crystallo-
graphically distinct molecules of similar geometries in the asym-
metric unit, respectively; the dimeric complexes 1 and 2 contain
one half of the molecule in the asymmetric unit with the other
half generated by an inversion center midway between the metal
centers; and for 6 the asymmetric unit contains one half of the
molecule and an MeNO2 solvent molecule with the other half of
6 generated by an inversion center at palladium.
The dimeric complexes 1 and 2 have configurations similar to
that of the chloro-analogue (II) [5c], e.g. bond angle ranges are
small for 1, 2, II (X–Pd–X (167.45(7)–174.58(4)°) and N–Pd–Se
(169.7(5)–176.82(9)°)). The pyridyl rings are inclined at 80.2(1)°
(X = Br) and 85.6(5)° (X = I) to the ‘X2NSe’ mean planes, and the
palladium atoms lie ꢀ0.195(5) Å (X = Cl), 0.037(6) Å (X = Br) and
0.23(3) Å (X = I) out of the ‘C5N’ mean plane. The displaced/step
configuration of the 10-membered rings are similar, illustrated
for X = I (Fig. 1(b)), and the PdX2 units are aligned to be crystallo-
graphically parallel.
and 36.2(2)°, 38.1(1)° for the two independent molecules in 8,
and 39:5ꢂ0 for the dibromo-complex.
3. Discussion
For palladium, methyl substitution in the 6-position results in
formation of complexes involving trans-PdX2NE units in dimers
for X = Br (1), I (2); dimer or trimer for X = Cl (III [5c]), and as
monomers for X = I (5, 6). In contrast, the congener platinum is
able to adopt cis-PtX2(N,E) monomeric structures for X = Cl (7,
8) and X = Br [1e]. The subtle interplay between the behavior of
palladium and platinum could possibly arise from several factors,
including identity of donor atoms, 6-Meꢃ ꢃ ꢃM interactions and
electronic factors. Clearly, the formation of the dimeric
structures is in response to removal of the strain in a chelating
arrangement introduced by the 6-Me group, and is one of the
ways that this series of complexes has been demonstrated to re-
spond under this influence. Other outcomes have included the
formation of trimers [5c] and the 2:1 ligand:MX2 products 5
and 6 discussed below.
For the larger iodo-donor and where the ligands pyCH2SePh and
4-MepyCH2SMe do not have a 6-methyl substituent (3, 4), the
bidentate configuration cis-PdI2(N,E) is accessable (Fig. 2(a) and
(b)). In contrast to the trimeric chloro-complex III, where a 6-
methyl substituent is present [5c], the analogous iodo-complex
for the same ligand forms a monomeric 2:1 complex with a
trans-PdI2N2 configuration with uncoordinated thioether groups
(6 Fig. 3(b)). The complex with closely related 6-MepyCH2SMe
(5) forms a similar structure (Fig. 3(a)). Complex 6, but not 5, has
an inversion center. Complex 5 has approximate C2v symmetry,
excepting the SMe substituent.
In the absence of a 6-Me substituent, the identity of the donor
atom appears to be unimportant to the structure that is adopted
by the complexes, e.g. as expected the donor atoms alternate above
and below the X2NE mean plane in all cis-MX2(N,E) complexes and
the average alternation is similar for cis-MCl2(N,S) (0.10–0.40 Å)
[5a–c], cis-PdCl2(N,Se) (0.1077 Å) [5c], cis-PtBr2(N,S) (0.250,
0.392 Å) [1e], and cis-PdI2(N,S) [0.067–0.618 (3), 0.266 Å (4)]. This
alternation is also unaffected by 6-Me substitution, as cis-PtCl2(N,S)
complexes have average deviations of 0.534 Å (7) and 0.128, 0.324 Å
(8), and cis-PtBr2(6-MepyCH2SMe) has an average deviation of
0.555 Å [1e].
The dichloroplatinum(II) complexes 7 and 8, both containing
ligands with a 6-methyl substituent, form mononuclear cis-PtCl2-
(N,S) motifs (Fig. 3), and have conformations similar to previously
reported PtBr2(6-MepyCH2SMe) [1e], including dihedral angles
between the pyridyl plane and coordination plane, 37.6(3)° for 7
In the platinum complexes (7, 8), steric interactions between
the 6-methyl group and the cis-related halogeno-donor are
clearly present, resulting in structures where the pyridyl ring
exhibits much larger dihedral angles with the coordination plane
[39:5ꢂ0 for cis-PtBr2(6-MepyCH2SMe) [1e] and 36.2(2)–38.1(2)° for
R4
SR1
Me
N
X2Pd
PhSe
SePh
PdX2
ER1
I
SR1
Cl
N
I
N
N
Me
Me
Pd
Pd
Pt
Me
I
I
N
Cl
N
Me
R1S
7 R1 = Me
8 R1 = Ph
1 X = Br
2 X = I
3 ER1 = SePh, R4 = Me
4 ER1 = SMe, R4 = H
5 R1 = Me
6 R1 = Ph
Scheme 2.

292
R.C. Jones et al. / Inorganica Chimica Acta 376 (2011) 290–295
Fig. 1. Projections of the dimers (a) [PdBr2(l-6-MepyCH2SePh-N,Se)]2 (1) and (b) [PdI2(l-6-MepyCH2SePh-N,Se)]2 (2) illustrating the conformation of the 10-membered
Pd2N2Se2C4 ring and trans-PdX2NE units.
Fig. 2. Projections of monomeric diiodopalladium(II) and dichloroplantinum(II) complexes; (a) one of three crystallographically independent molecules of PdI2(pyCH2SePh-
N,E) (3), (b) PdI2(4-MepyCH2SMe-N,E) (4), (c) PtCl2(6-MepyCH2SMe-N,S) (7), and (d) one of two crystallographically independent molecules of PtCl2(6-MepyCH2SPh-N,S) (8).
7, 8] than in cis-MX2(N,E) complexes lacking a 6-Me group
and 0.29(1), 0.20(1) Å for 8, compared with 0.002(9) Å for the
4-Me group in 4. As noted above for the dimeric complexes 1
and 2, the 6-Me group destabilises the chelate ring. However,
in the case of 7 and 8, not sufficiently so as to bring about this
change to the binding mode.
The combination of large iodine atoms and 6-Me groups leads
to either dimeric (2) or monomeric structures (5, 6), with very
similar trans-PdI2N2 configurations.
[13.14–17:7ꢂ [1e,5a,5c], 13.3(2)–23.2(1)° (3), 15.9(2)° (4)],
7
illustrated in Fig. 2(a) and (b). In a similar manner, the carbon
atom of the methylene bridge is further removed from the cis-
X2(N,E) mean plane when a 6-Me group is present (0.48–0.81 Å
[1e,5a–c]; 0.514(9), 0.712(8), 0.876(8) Å in 3; 0.613(7) Å in 4;
compared with 1.18(1) Å in (7) and 1.171(9), 1.190(8) Å in 8).
Congestion in 6-Me derivatives is also reflected in the deviation
of the C atom of the 6-Me group from the pyridyl C5N mean
plane, 0.179 Å for cis-PtBr2(6-MepyCH2SMe) [1e], 0.18(2) Å for 7
Adoption of different structures for palladium and platinum
when a 6-methyl substituent is present does not appear to be

R.C. Jones et al. / Inorganica Chimica Acta 376 (2011) 290–295
293
Fig. 3. Projections of 2:1 diiodopalladium(II) complexes (a) PdI2(6-MepyCH2SMe-N)2 (5), and (b) PdI2(6-MepyCH2SPh-N)2 (6).
the adoption of different alternatives to the monomeric PdX2(N,E)
configuration, i.e. dimers containing the trans-PdX2(N,Se) motif,
trimer containing trans-PdCl2(N,S) and 2:1 monomers with trans-
PdI2N2 coordination environments.
Table 1
Selected bond distances and angles for [PdBr2(
[PdI2(l-6-MepyCH2SePh-N,Se)]2 (2).
l
-6-MepyCH2SePh-N,Se)]2 (1) and
(2)
(1)
Bond distances (Å)
Pd–N(1)
Pd–Se(1)
Pd–X(1)
Pd–X(2)
2.062(4)
2.066(15)
2.404(2)
2.6207(19)
2.613(2)
4. Experimental
2.4000(6)
2.4260(7)
2.4331(7)
All manipulations were carried out under argon using standard
Schlenk techniques. The ligands pyCH2SePh, 6-MepyCH2SPh, 6-Me-
pyCH2SePh [5c], 6-MepyCH2SMe and 4-MepyCH2SMe [1e] were
prepared as reported; all other reagents and solvents were
obtained from the Aldrich Chemical Co. and were used as received
unless specified. Ultra high purity argon was purchased from BOC
Gases. Microanalyses were performed by Dr. Thomas Rodemann of
the Central Science Laboratory (CSL), University of Tasmania using
a ThermoFinnigan Flash EA 1112 Series Elemental Analyser. Mass
spectrometry was conducted by Assoc. Prof. Noel Davies and Dr.
Marshall Hughes of the CSL. The LSIMS (Liquid Secondary Ionisa-
tion Mass Spectrometry) were carried out using a Kratos ISQ mass
spectrometer with a liquid matrix of nitrobenzyl alcohol using
10 kV Cs ions and a 5.3 kV accelerating voltage.
Bond angles (°)
N(1)–Pd–Se(1)
N(1)–Pd–X(1)
N(1)–Pd–X(2)
Se(1)–Pd–X(1)
Se(1)–Pd–X(2)
X(1)–Pd–X(2)
Pd–Se(1)–C(H2)
Pd–Se(1)–C(Ar)
C(H2)–Se(1)–C(Ar)
170.32(11)
89.06(11)
89.65(11)
96.716(19)
85.544(18)
172.92(2)
108.64(14)
106.67(14)
96.0(2)
169.7(5)
89.8(4)
89.7(4)
85.47(7)
96.89(7)
167.45(7)
109.5(5)
107.3(5)
97.4(8)
Table 2
Selected bond distances and angles for complexes containing mononuclear trans-
PdI2N2 motifs, PdI2(6-MepyCH2SMe)2 (5), and PdI2(6-MepyCH2SPh) (6).
(5)
(6)
4.1. Synthesis of complexes
Bond distances (Å)
Pd–N(1)
Pd–N(2)
2.050(3)
2.050(4)
2.080(11)
–
4.1.1. PdBr2(6-MepyCH2SePh) (1)
A suspension of PdBr2 (0.10 g, 0.38 mmol) and 6-MepyCH2SePh
(0.11 g, 0.42 mmol, 1.1 eq.) in dry acetonitrile (25 mL) was stirred
for 12 h at room temperature to give an orange solution. The vol-
ume was reduced to ca. 5 mL in a vacuum, and diethyl ether added
to precipitate the orange solid which was collected by filtration
and washed with diethyl ether (0.17 g, 83%). Anal. Calc. C, 22.55;
H, 2.48; N, 2.65. Found: C, 22.59; H, 2.54; N, 2.53%. LSIMS m/z
Pd–I(1)
Pd–I(2)
2.6278(4)
2.6219(4)
2.6191(9)
–
Bond angles (°)
N(1)–Pd–N(2), N(1)0
N(1)–Pd–I(1)
N(1)–Pd–I(2), I(1)0
N(2)–Pd–I(1)
178.47(13)
90.04(11)
89.94(11)
90.17(10)
89.84(10)
179.600(14)
180
87.8(3)
92.2(3)
–
–
180
N(2)–Pd–I(2)
I(1)–Pd–I(2), I(1)0
448 [1/2 MꢀBr]+, [12C13 H1379Br14N79Se106Pd 448].
1
4.1.2. PdI2(L) (2–6)
solely as a result of Meꢃ ꢃ ꢃX interaction since, for isomorphous
MCl2(pyCH2SePh) [5a], intramolecular C(6)ꢃ ꢃ ꢃCl and H(6)ꢃ ꢃ ꢃCl dis-
tances are essentially identical, 3.212, 2.571 Å (Pd) and 3.189,
2.572 Å (Pt). However, the significant change in configuration of
platinum complexes on 6-methyl substitution do indicate the
presence of steric effects. It is assumed that electronic factors play
a more significant role for palladium than platinum, resulting in
Suspensions of PdI2 (0.10 g, 0.28 mmol) and ligand (0.31 mmol,
(0.62 mmol in the case of complexes 5 and 6)) in dry acetonitrile
(25 mL) were stirred for 12 h at room temperature to give dark
purple solutions (a yellow solution was observed in the case of
complex 2). The volume was reduced to ca. 5 mL in a vacuum,
and diethyl ether added to precipitate the complexes which were
collected by filtration and washed with diethyl ether.

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R.C. Jones et al. / Inorganica Chimica Acta 376 (2011) 290–295
Table 3
Selected bond distances and angles for complexes containing mononuclear MX2(N,E) motifs, PdI2(pyCH2SePh) (3), PdI2(4-MepyCH2SMe) (4), PtCl2(6-MepyCH2SMe) (7), and
PtCl2(6-MepyCH2SPh) (8).
(3)
(4)
(7)
(8)
Bond distances (Å)
M–N(1)
M–E(1)
M–X(1)
M–X(2)
2.113(5), 2.128(6), 2.095(5)
2.098(5)
2.054(13)
2.250(4)
2.336(3)
2.296(4)
2.055(6), 2.067(6)
2.239(2), 2.245(2)
2.331(2) 2.312(2)
2.293(2), 2.296(2)
2.3803(10), 2.3686(12), 2.3911(10)
2.5999(10), 2.5979(11), 2.6004(9)
2.5772(11), 2.5934(10), 2.5711(11)
2.2765(14)
2.6236(5)
2.5816(5)
Bond angles (°)
N(1)–M–E(1)
N(1)–M–X(1)
N(1)–M–X(2)
E(1)–M–X(1)
E(1)–M–X(2)
X(1)–M–X(2)
M–E(1)–C(H2)
M–E(1)–C(CH3,Ar)
C(H2)–E(1)–C(CH3,Ar)
85.62(14), 86.23(14), 84.71(15)
96.85(14), 96.68(14), 96.12(15)
169.30(15), 173.26(14), 172.34(15)
173.61(3), 176.93(3), 179.08(3)
88.75(4), 87.06(3), 88.54(3)
89.71(4), 90,04(3), 90.61(3)
93.0(2), 94.7(2), 90.9(2)
84.90(13)
96.72(12)
170.57(12)
178.20(4)
87.55(4)
90.915(17)
97.31(19)
103.6(2)
84.2(4)
96.8(4)
83.33(17), 83.72(18)
96.19(17), 96.49(18)
174.05(17), 172.57(18)
170.90(7), 172.29(8)
90.74(8), 90.21(8)
89.58(8), 88.95(8)
92.8(3), 92.3(3)
173.6(3)
167.91(12)
89.80(15)
89.53(14)
91.3(4)
105.7(2), 101.9(2), 102.4(2)
99.3(3), 101.0(3), 97.0(3)
107.9(5)
100.1(7)
109.4(2), 110.1(3)
102.2(4), 102.0(4)
100.4(3)
Chelate ring torsion angles (°)
E–M–N–C
M–N–C–C
N–C–C–E
C–C–E–M
C–E–M–N
Me/Ar–E–M–N
Me/Ar–E–C–C
ꢀ9.3(5), ꢀ14.0(4), 17.4(4)
ꢀ14.5(8), 4.0(8), 8.3(8)
9.7(4)
28.2(8)
31.8(5), 31.1(5)
ꢀ8.3(8), ꢀ7.8(9)
ꢀ28.3(8), ꢀ28.4(9)
44.7(5), 44.2(6)
ꢀ37.5(3), ꢀ36.7(3)
66.5(3), 67.0(3)
10.1(7)
ꢀ30.7(7)
32.4(4)
ꢀ20.7(2)
81.9(3)
ꢀ73.0(5)
ꢀ2.5(15)
ꢀ34.7(15)
47.7(9)
36.2(8), 12.1(9), ꢀ36.8(7)
ꢀ35.1(5), ꢀ18.6(6), 40.5(5)
21.4(3), 15.0(3), ꢀ27.5(2)
ꢀ79.2(3), ꢀ87.3(3), 69.9(2)
71.3(3), 84.5(6), ꢀ62.1(5)
ꢀ37.3(5)
63.7(6)
ꢀ60.8(11)
ꢀ65.8(6), ꢀ66.9(7)
Interplanar dihedral angles (°) and out-of-plane deviations (dÅ)
C5N/X2EN
C6/X2EN
dMepy/C5N
dM/C5N
dM/X2EN
dN/X2EN
23.2(1), 13.3(2), 21.0(3)
89.5(2), 84.2(2), 84.0(1)
–
0.33(1), ꢀ0.28(1), ꢀ0.19(1)
ꢀ0.022(2), 0.005(2), 0.041(2)
0.566(5), 0.062(5), ꢀ0.118(5)
ꢀ0.562(5), ꢀ0.061(5), 0.118(5)
ꢀ0.676(6), ꢀ0.074(6), 0.143(6),
0.668(6), 0.072(6), ꢀ0.143(6)
ꢀ0.712(8), ꢀ0.514(9), 0.876(8)
15.9(2)
–
37.6(3)
–
0.18(2)
0.059(18)
0.107(3)
0.507(9)
ꢀ0.499(9)
ꢀ0.571(11)
0.561(10)
ꢀ1.18(1)
38.1(2), 36.2(2)
79.9(2), 81.5(2)
0.002(9)
0.223(7)
ꢀ0.047(1)
0.241(5)
ꢀ0.232(5)
ꢀ0.303(6)
0.289(6)
ꢀ0.613(7)
ꢀ0.29(1), ꢀ0.20(1)
0.26(1), 0.30(1)
ꢀ0.100(2), ꢀ0.121(2)
ꢀ0.304(7), ꢀ0.122(7)
0.302(7), 0.120(6)
0.347(7), 0.137(8)
ꢀ0.344(7), ꢀ0.135(7)
1.190(9), 1.171(9)
dE/X2EN
dX(1)/X2EN
dX(2)/X2EN
d(CH2)/X2EN
Table 4
Crystal/refinement data.
Complex
Formula
1
2
3
4
5
6
7
8
C
26H26Br4N2Pd2Se2 C26H26I4N2Pd2Se2 C12H11I2NPdSe C8H11I2NPdS
C16H22I2N2PdS2 C26H26I2N2PdS2.
CH3NO2
C8H11Cl2NPtS C13H13Cl2NPtS
Mr (Da)
Crystal system monoclinic
Space group
1056.85
1244.81
triclinic
608.38
triclinic
513.44
orthorhombic triclinic
Pbca
666.68
851.85
monoclinic
C2/c
419.23
monoclinic
P21/n
481.29
triclinic
ꢀ
ꢀ
ꢀ
ꢀ
P21/c
P1
P1
P1
P1
a (Å)
b (Å)
c (Å)
11.8260(10)
8.4930(14)
15.8940(17)
–
109.354(12)
–
1506.2(3)
2.330
8.097(4)
9.357(2)
10.834(2)
88.039(12)
79.86(3)
75.580(9)
782.5(5)
2.642
9.307(3)
13.179(3)
19.213(5)
77.896(17)
81.24(3)
88.83(3)
2277.0(11)
2.662
6
7.7
0.32, 0.26,
0.26
9.0600(10)
15.2100(2)
18.3100(2)
–
–
–
2523.17(5)
2.703
8
6.5
0.08, 0.02,
0.01
8.0430(10)
8.8900(6)
15.7690(13)
88.370(3)
84.081(4)
65.095(3)
1017.08(17)
2.177
17.349(4)
8.0412(16)
21.617(4)
–
91.65(3)
–
3014.3(10)
1.877
4
8.162(2)
8.446(14)
16.243(7)
–
97.06(3)
–
1111.2(19)
2.506
4
9.3063(11)
9.649(2)
16.878(12)
82.44(4)
87.18(3)
83.180(12)
1490.9(12)
2.144
4
9.9
0.30, 0.20,
0.20
a
(°)
b (°)
c
(°)
V (Å3)
Dcalc (g cmꢀ3
)
Z
2
8.9
1
7.4
2
4.2
lMo (mmꢀ1
Specimen
(mm3)
)
2.8
13.2
0.25, 0.22,
0.22
0.04, 0.04, 0.02
0.05, 0.05, 0.03
0.05, 0.05, 0.05 0.40, 0.20, 0.16
2hmax (°)
Nt
51
51
8711
50
8093
51
26 109
52
11 055
50
2615
50
2090
50
5453
15 301
2264(0.0953)
2246
0.0354
0.0886
1.070
N (Rint
)
2251(0.0383)
2095
0.0890
0.2335
1.077
7831(0.0285)
6712
0.0356
0.0883
1.069
1998(0.0334) 2876(0.0598)
1900
0.0310
0.0777
1.091
2565(0.0534)
2192
0.0729
0.0234
1.161
1944(0.0917) 5260(0.0265)
1533
0.0595
0.1612
1.019
No
R
wR
S
2768
4274
0.0332
0.0888
1.068
0.0319
0.0759
1.017
4.1.2.1. [PdI2(
l
-6-MepyCH2SePh-N,Se)]2 (2). Yellow solid (0.15 g,
4.1.2.2. PdI2(pyCH2 SePh-N,E) (3). Purple solid (0.16 g, 92%):
Anal. Calc. C, 23.69; H, 1.82; N, 2.30. Found: C, 23.42; H,
87%): Anal. Calc. C, 22.09; H, 2.11; N, 2.25. Found: C, 22.14; H,
2.17; N, 2.28%. LSIMS m/z 496 [1/2 MꢀI]+, [12C13 H13126I14N79-
1.67; N, 2.22%. LSIMS m/z 481 [MꢀI]+, [12C12 H11126I14N79Se106Pd
1
1
Se106Pd 496].
481].

R.C. Jones et al. / Inorganica Chimica Acta 376 (2011) 290–295
295
4.1.2.3. PdI2(4-Me-pyCH2 SMe-N,S) (4). Purple solid (0.14 g, 97%):
Appendix A. Supplementary material
Anal. Calc. C, 18.71; H, 2.16; N, 2.73. Found: C, 18.78; H, 2.19; N,
2.75%. LSIMS m/z 387 [MꢀI]+, [12C8 H11126I14N32S106Pd 387].
1
CCDC 810125, 810126, 810127, 810128, 810129, 810130,
810131 and 810132 contain the supplementary crystallog-
raphic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
4.1.2.4. PdI2(6-MepyCH2SMe-N)2 (5). Purple solid (0.16 g, 85%):
Anal. Calc. C, 28.82; H, 3.33; N, 4.20. Found: C, 28.88; H, 3.38; N,
1
4.15%. LSIMS m/z 540 [MꢀI]+, [12C16 H22
I
126 14N232S2106Pd 540].
References
4.1.2.5. PdI2(6-MeCH2SPh-N)2 (6). Purple solid (0.19 g, 87%): Anal.
Calc. C, 39.49; H, 3.31; N, 3.54. Found: C, 39.54; H, 3.40; N,
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1
4.1.3. PtCl2(L) (7, 8)
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1
384].
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1
446].
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0.95 (sp2CH), 0.99 (CH2), 0.98 Å (CH3). The thermal parameters of
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Acknowledgments
We thank the Australian Research Council for financial support,
Assoc. Prof. Noel Davies and Dr. Thomas Rodemann of the Central
Science Laboratory for mass spectrometry and elemental analysis
of complexes. Aspects of this research were undertaken on the
MX1 beamline at the Australian Synchrotron, Victoria, Australia.