Structural and spectroscopic trends in mononuclear arylchalcogenolato-palladium(II) and -platinum(II) complexes: Crystal structures of [M(TeAr)2(dppe)] {M = palladium, platinum; Ar = phenyl, 2-thienyl; dppe = 1,2-bis(diphenylphosphino)ethane}

Article abstract of DOI:10.1016/j.jorganchem.2007.01.039

A series of mononuclear [M(EAr)₂(dppe)] [M = Pd, Pt; E = Se, Te; Ar = phenyl, 2-thienyl; dppe = 1,2-bis(diphenylphosphino)ethane] complexes has been prepared in good yields by the reactions of [MCl₂(dppe)] and corresponding ArE^- with a special emphasis on the aryltellurolato palladium and -platinum complexes for which the existing structural information is virtually non-existent. The complexes have crystallized in five isomorphic groups: (1) [Pd(SePh)₂(dppe)] and [Pt(SePh)₂(dppe)], (2) [Pd(TePh)₂(dppe)] and [Pt(TePh)₂(dppe)], (3) [Pd(SeTh)₂(dppe)], (4) [Pt(SeTh)₂(dppe)] and [Pd(TeTh)₂(dppe)], and (5) [Pt(TePh)₂(dppe)]. In addition, solvated [Pd(TePh)₂(dppe)] · CH₃OH and [Pd(TeTh)₂(dppe)] · 1/2CH₂Cl₂ could be isolated and structurally characterized. The metal atom in each complex exhibits an approximate square-planar coordination. The Pd-Se, Pt-Se, Pd-Te, and Pt-Te bonds span a range of 2.4350(7)-2.4828(7) A?, 2.442(1)-2.511(1) A?, 2.5871(7)-2.6704(8) A?, and 2.6053(6)-2.6594(9) A?, respectively, and the respective Pd-P and Pt-P bond distances are 2.265(2)-2.295(2) A? and 2.247(2)-2.270(2) A?. The orientation of the arylchalcogenolato ligands with respect to the M(E₂)(P₂) plane has been found to depend on the E-M-E bond angle. The NMR spectroscopic information indicates the formation of only cis-[M(EAr)₂(dppe)] complexes in solution. The trends in the ³¹P, ⁷⁷Se, ¹²⁵Te, and ¹⁹⁵Pt chemical shifts expectedly depend on the nature of metal, chalcogen, and aryl group. Each trend can be considered independently of other factors. The ⁷⁷Se or ¹²⁵Te resonances appear as second-order multiplets in case of palladium and platinum complexes, respectively. Spectral simulation has yielded all relevant coupling constants.

Full text of DOI:10.1016/j.jorganchem.2007.01.039

Journal of Organometallic Chemistry 692 (2007) 2193–2204
www.elsevier.com/locate/jorganchem
Structural and spectroscopic trends in mononuclear
arylchalcogenolato-palladium(II) and -platinum(II) complexes:
Crystal structures of [M(TeAr)2(dppe)] {M = palladium,
platinum; Ar = phenyl, 2-thienyl;
dppe = 1,2-bis(diphenylphosphino)ethane}
*
Maarit Risto, Esther M. Jahr, Milja S. Hannu-Kuure, Raija Oilunkaniemi ,
*
Risto S. Laitinen
Department of Chemistry, University of Oulu, P.O. Box 3000, FI-90014 Oulu, Finland
Received 15 December 2006; received in revised form 21 January 2007; accepted 22 January 2007
Available online 30 January 2007
Abstract
A series of mononuclear [M(EAr)2(dppe)] [M = Pd, Pt; E = Se, Te; Ar = phenyl, 2-thienyl; dppe = 1,2-bis(diphenylphosphino)eth-
ane] complexes has been prepared in good yields by the reactions of [MCl2(dppe)] and corresponding ArEꢀ with a special emphasis
on the aryltellurolatopalladium and -platinum complexes for which the existing structural information is virtually non-existent. The com-
plexes have crystallized in five isomorphic groups: (1) [Pd(SePh)2(dppe)] and [Pt(SePh)2(dppe)], (2) [Pd(TePh)2(dppe)] and
[Pt(TePh)2(dppe)], (3) [Pd(SeTh)2(dppe)], (4) [Pt(SeTh)2(dppe)] and [Pd(TeTh)2(dppe)], and (5) [Pt(TePh)2(dppe)]. In addition, solvated
[Pd(TePh)2(dppe)] Æ CH3OH and [Pd(TeTh)2(dppe)] Æ 1/2CH2Cl2 could be isolated and structurally characterized. The metal atom in each
complex exhibits an approximate square-planar coordination. The Pd–Se, Pt–Se, Pd–Te, and Pt–Te bonds span a range of 2.4350(7)–
˚
˚
˚
˚
2.4828(7) A, 2.442(1)–2.511(1) A, 2.5871(7)–2.6704(8) A, and 2.6053(6)–2.6594(9) A, respectively, and the respective Pd–P and Pt–P
˚
˚
bond distances are 2.265(2)–2.295(2) A and 2.247(2)–2.270(2) A. The orientation of the arylchalcogenolato ligands with respect to the
M(E2)(P2) plane has been found to depend on the E–M–E bond angle. The NMR spectroscopic information indicates the formation
of only cis-[M(EAr)2(dppe)] complexes in solution. The trends in the 31P, 77Se, 125Te, and 195Pt chemical shifts expectedly depend on
the nature of metal, chalcogen, and aryl group. Each trend can be considered independently of other factors. The 77Se or 125Te reso-
nances appear as second-order multiplets in case of palladium and platinum complexes, respectively. Spectral simulation has yielded
all relevant coupling constants.
ꢀ 2007 Elsevier B.V. All rights reserved.
Keywords: Organotellurium ligands; Organoselenium ligands; Palladium complexes; Platinum complexes; X-ray crystallography; NMR spectroscopy
1. Introduction
addition to alkynes involves a dinuclear palladium interme-
diate [Pd2(EAr)4L2] (E = S, Se; L = phosphine or a related
ligand) [1–6]. Such complexes have been isolated after the
oxidative addition of Ar2E2 to [PdL4] or substitution reac-
tion of the chloride ligands in [PdCl2L2] by ArEꢀ [7–10].
The reaction utilizing the Pt(0) catalyst seems to proceed
with a different mechanism, since platinum does not show
as good propensity for the formation of polynuclear
complexes as palladium [2]. It has been suggested that
The role of chalcogenolato complexes of palladium and
platinum in the Pd(0) and Pt(0) catalyzed reactions of
Ar2S2 and Ar2Se2 with alkynes has recently been discussed
[1–6]. In case of the Pd(0) catalyst, the S–S or Se–Se bond
*
Corresponding authors. Fax: +358 8 553 1608 (R.S. Laitinen).
E-mail address: Risto.Laitinen@oulu.fi (R.S. Laitinen).
0022-328X/$ - see front matter ꢀ 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2007.01.039

2194
M. Risto et al. / Journal of Organometallic Chemistry 692 (2007) 2193–2204
mononuclear cis-[Pt(EAr)2L2] complexes are catalytically
active, but the catalyst degrades with time because of the
formation of the trans-isomer [2].
[22]} the only crystal structure of the series determined to
date is that of [Pd(SePh)2(dppe)] Æ C6H6 [24].
We have recently investigated the ligand substitution
reactions of different arylselenolates with trans-[PdCl2-
(PPh3)2] and cis-[PtCl2(PPh3)2]. Whereas the reactions
involving palladium afforded solely dinuclear [Pd2(SeAr)4-
(PPh3)2] [11–13], those involving cis-[PtCl2(PPh3)2] initially
produced cis-[Pt(SeAr)2(PPh3)2] that subsequently under-
went facile isomerization from cis to trans form in solution
[14,15]. The DFT calculations of model [Pt(SeAr)2(PH3)2]
(Ar = Ph, 2-thienyl, 2-furyl) isomers indicated that the
cis-isomers indeed lie at higher energy than the trans-
isomers [15] providing a rationale for the cis–trans
interconversion.
Similar product distributions and equally facile isomer-
ization have been observed in the reactions of [Pd(PPh3)4]
and [Pt(PPh3)4] with Ar2Se2 [2,7,16]. It has also been
reported that the oxidative addition of Ar2Te2 to
[Pd(PPh3)2] affords a dinuclear complex [17,18], though
the reaction has also been shown to produce hexanuclear
complexes [16].
2. Experimental
2.1. General
All reactions and manipulations of air- and moisture-
sensitive reagents were carried out under an inert atmo-
sphere by using a standard glovebox or Schlenk techniques.
[PdCl2(dppe)] (Aldrich), Ph2Se2 (Aldrich), Ph2Te2
(Aldrich), n-butyl lithium (2.5 M in hexanes, Aldrich), tel-
lurium (Aldrich), and selenium (Merck) were used as sup-
plied. [PtCl2(dppe)] was prepared by the method of
Appleton et al. [26]. Thiophene (Aldrich) was purified by
distillation and purged with argon before use. Methanol
was dried on molecular sieves and degassed with argon.
Toluene and n-hexane were dried by distillation over Na/
benzophenone and CH2Cl2 was dried over P4O10 under
an argon atmosphere prior to use.
2.2. Synthesis of [M(EAr)2(dppe)] (1)–(8)
Interestingly, the cis–trans isomerization of mononu-
clear selenolato complexes seems to be dependent on
the electron-withdrawing power of the organic substituent
bonded to selenium, since the related cis-[Pt(SeR)2-
2.2.1. [Pd(SePh)2(dppe)] (1)
0.089 g (0.285 mmol) of Ph2Se2 in 5 ml of methanol
was treated with NaBH4 until the solution became trans-
parent. The resulting solution was added to a suspension
of 0.149 g (0.260 mmol) of [PdCl2(dppe)] in 10 ml toluene.
The reaction mixture was stirred overnight at room tem-
perature. Volatile materials were removed under dynamic
vacuum. The red solid residue was dissolved in dichloro-
methane (10 ml), filtered, and concentrated by partial
evaporation of the solvent. [Pd(SePh)2(dppe)] was precip-
itated by adding n-hexane into the solution. The orange
solid product was filtered off, washed with hexane and
dried. Isolated yield 0.131 g (62%). Anal. Calc. for
C38H34P2Se2Pd: C, 55.86; H, 4.20. Found: C, 54.65; H,
4.30%.
t
(PPh3)2] (R = nBu, Bu) do not seem to undergo isomeri-
zation [19], though the DFT calculations of model
[Pt(SeR)2(PH3)2] isomers indicate that the cis-isomers lie
at higher relative energy than the trans-isomers even in
the alkyselenolato complexes [15]. Evidently, the solvent
also plays a role. Isomerization of cis-[Pt(SeCF3)2(PPh3)2]
with electronegative trifluoromethylselenolato ligands to
the trans-form takes place rapidly in dichloromethane,
but the process in acetonitrile is much slower [20]. While
the investigations of the analogous tellurolato complexes
are sparse [20,21], it has been reported that, contrary to
the analogous selenolato complex, there was no evidence
of the isomerization of cis-[Pt(TeCF3)2(PPh3)2] to the
trans form [20].
The formation of dinuclear palladium complexes is
avoided by using a chelating phosphine ligand [22–25]
and it also forces the formation of only the cis-isomer. It
has been reported that [M(SAr)2(dppe)] and [M(SeAr)2-
(dppe)] [M = Pd, Pt; Ar = Ph; dppe = 1,2-bis(diphenyl-
phosphino)ethane] are virtually catalytically inactive for
the addition of Ar2E2 to alkynes [2], but it is an open ques-
tion, whether the replacement of sulfur or selenium by tel-
lurium would lead to improved catalytic properties of the
complexes.
Complexes 2–4 were prepared in a similar fashion to
1.
2.2.2. [Pt(SePh)2(dppe)] (2)
0.172 g (0.260 mmol) of [PtCl2(dppe)] and 0.089 g
(0.285 mmol) of Ph2Se2. Yield 0.130 g (55%). Yellow solid.
Anal. Calc. for C38H34P2Se2Pt: C, 50.39; H, 3.78. Found:
C, 50.11; H, 3.64%.
2.2.3. [Pd(TePh)2(dppe)] (3)
0.251 g (0.436 mmol) [PdCl2(dppe)] and 0.200 g
(0.489 mmol) Ph2Te2. Yield 0.249 g (63%). Reddish brown
solid. Anal. Calc. for C38H34P2Te2Pd: C, 49.92; H, 3.75.
Found: C, 49.08; H 3.63%.
In order to further explore the chemistry of chalcogeno-
lato complexes of palladium and platinum, we report here
a study of the synthesis, NMR spectroscopic properties,
and crystal structures of a series of [M(EAr)2(dppe)]
(M = Pd, Pt; E = Se, Te; Ar = Ph, 2-thienyl). While the
preparations of [M(EPh)2(dppe)] (M = Pd, Pt; E = Se,
Te) have been reported previously {E = Se [22–24], Te
2.2.4. [Pt(TePh)2(dppe)] (4)
0.131 g (0.197 mmol) [PtCl2(dppe)] and 0.089 g
(0.217 mmol) Ph2Te2. Stirred for 2 h. Yield 0.084 g (42%).

M. Risto et al. / Journal of Organometallic Chemistry 692 (2007) 2193–2204
2195
Orange solid. Anal. Calc. for C38H34P2Te2Pt: C, 45.50; H,
2.2.7. [Pd(TeTh)2(dppe)] (7)
3.42. Found: C, 45.54; H 3.32%.
0.249 g (0.432 mmol) [PdCl2(dppe)] and 0.950 mmol
LiTeTh. Stirred overnight. Yield 0.301 g (75%). Purple
solid. Anal. Calc. for C38H34P2Te2Pd: C, 44.08; H, 3.26;
S, 6.92. Found: C, 44.22; H, 3.31; S, 6.81%.
2.2.5. [Pd(SeTh)2(dppe)] (5)
1.5 ml (3.75 mmol) n-BuLi was added to a solution of
0.33 ml (4.12 mmol) of thiophene in 8 ml of THF. Freshly
ground selenium (0.281 g, 3.56 mmol) was added into the
reaction solution after 30 min. The reaction mixture was
stirred at room temperature for further 40 min. 4.00 ml
of the resulting LiSeTh solution (1.45 mmol) was added
to a solution of [PdCl2(dppe)] (0.386 g, 0.67 mmol) in
15 ml of CH2Cl2. The reaction mixture was stirred for
2 h, filtered, and concentrated by a partial evaporation
of the solvent. [Pd(SeTh)2(dppe)] was precipitated by
adding n-hexane into the solution. The orange product
was filtered off, washed with n-hexane and dried. Yield
0.496 g (94%). Anal. Calc. for C34H30P2S2Se2Pd: C,
46.02; H, 4.12; S, 8.19. Found: C, 46.23; H, 3.87; S,
7.40%.
2.2.8. [Pt(TeTh)2(dppe)] (8)
0.100 g (0.151 mmol) [PtCl2(dppe)] and 0.331 mmol
LiTeTh. Yield 0.070 g (46%). Orange solid. Anal. Calc.
for C38H34P2Te2Pt: C, 40.23; H, 2.98; S, 6.32. Found: C,
39.76; H, 2.85; S, 6.33%.
2.3. NMR spectroscopy
The 31P{1H}, 77Se, 125Te, and 195Pt NMR spectra were
recorded in CH2Cl2 on a Bruker DPX400 spectrometer
operating at 161.98, 76.31, 126.29, and 85.57 MHz, respec-
tively. The typical respective spectral widths were 48.543,
100.000, 100.000, and 85.47 kHz, and the respective pulse
widths were 7.50, 6.70, 6.67, and 10.00 ls. The pulse delays
were 1.0, 2.0, 1.5, and 0.01 s for 31P, 77Se, 125Te, and 195Pt,
respectively. Orthophosphoric acid (85%), saturated solu-
tions of SeO2 (aq) and H6TeO6 (aq), and K2PtCl6 in D2O
were used as external standards. The 31P and 195Pt chemical
shifts are reported relative to the external standards, and
the 77Se and 125Te chemical shifts relative to neat Me2Se
Complexes 6–8 were prepared in a similar fashion to 5.
2.2.6. [Pt(SeTh)2(dppe)] (6)
0.153 g (0.230 mmol) [PtCl2(dppe)] and 0.507 mmol
LiSeTh. Yield 0.093 g (46%). Yellow solid. Anal. Calc.
for C38H34P2Se2Pt: C, 44.50; H, 3.30; S, 6.99. Found: C,
43.63; H, 3.31; S, 7.16%.
Table 1
Details of the crystal structure determination of complexes 1–4
1
2
3
3 Æ CH3OH
4
Empirical formula
Relative molecular mass
Crystal system
C
816.91
Monoclinic
P21/n
17.943(4)
11.563(2)
32.161(6)
95.06(3)
6647(2)
8
38H34P2PdSe2
C38H34P2PtSe2
905.60
Monoclinic
P21/n
17.925(4)
11.535(2)
32.199(6)
95.03(3)
6632(2)
C38H34P2PdTe2
914.19
Monoclinic
P21/c
10.451(2)
15.395(3)
21.736(4)
96.19(3)
3477(1)
C39H38OP2PdTe2
946.23
Monoclinic
P21/n
10.106(2)
16.058(3)
23.519(5)
96.90(3)
3789(1)
C38H34P2PtTe2
1002.88
Monoclinic
P21/c
10.480(2)
15.260(3)
21.753(4)
96.30(3)
3458(1)
Space group
˚
a (A)
˚
b (A)
˚
c (A)
b (ꢁ)
3
˚
V (A )
Z
8
4
4
4
F (000)
3248
1.633
2.872
0.20 · 0.20 · 0.20
2.99–26.00
49101
3504
1.814
6.550
0.25 · 0.20 · 0.05
3.00–25.00
37481
1768
1.747
2.296
0.30 · 0.15 · 0.05
2.47–26.00
20688
1840
1.659
2.112
0.20 · 0.20 · 0.10
3.08–26.00
59149
1896
1.926
5.830
0.50 · 0.15 · 0.10
3.13–26.00
50249
Dcalc (g cmꢀ3
)
l (Mo Ka) (mmꢀ1
Crystal size (mm)
h Range (ꢁ)
)
Number of reflections
collected
Number of unique reflections
Number of observed
reflectionsa
12987
10247
10836
9101
6702
5199
7411
6435
6767
6304
Number of parameters
Rint
776
776
388
415
388
0.0811
0.0445
0.1101
1.028
0.0779
0.0472
0.1208
1.013
0.0692
0.0480
0.1389
1.171
0.1426
0.0579
0.1612
1.108
0.0699
0.0343
0.0922
1.055
b
R1
wR2 (all data)b
Goodness-of-fit
Maximum and minimum
0.906, ꢀ0.806
1.570, ꢀ1.736
0.936, ꢀ1.288
2.322, ꢀ1.982
2.139, ꢀ1.828
heights in final difference
ꢀ3
˚
Fourier synthesis (e A
)
a
I P 2r(I).
P
P
P
P
2
1=2
b
R1 = ||Fo| ꢀ |Fc||/ |Fo|, wR2 ¼ ½ wðF 2o ꢀ F c2Þ = wF o4ꢁ
.

2196
M. Risto et al. / Journal of Organometallic Chemistry 692 (2007) 2193–2204
Table 2
Details of the crystal structure determination of complexes 5–8
5
6
7
7 Æ 1/2CH2Cl2
8
Empirical formula
Relative molecular mass
Crystal system
C
828.96
Orthorhombic
P212121
34H30P2PdS2Se2 C34H30P2PtS2Se2 C34H30P2PdS2Te2 C34.50H31ClP2PdS2Te2 C34H30P2PtS2Te2
917.65
Monoclinic
P21
926.24
Monoclinic
P21
968.70
Monoclinic
P21/n
1014.93
Monoclinic
P21/c
Space group
˚
a (A)
11.655(2)
16.465(3)
17.156(3)
9.542(2)
16.990(3)
10.290(2)
108.61(3)
1581.0(6)
2
9.650 (29)
16.997(3)
10.567(2)
108.60(3)
1642.7(6)
2
11.029(2)
20.924(4)
15.224(3)
93.63(3)
3506 (1)
4
11.926(2)
16.098(3)
17.080(3)
97.07(3)
3254(1)
4
˚
b (A)
˚
c (A)
b (ꢁ)
3
˚
V (A )
3292(1)
4
Z
F (000)
1640
1.672
3.022
884
1.928
6.997
892
1.873
2.554
1868
1.835
2.471
1912
2.072
6.320
0.20 · 0.20 · 0.05
3.05–26.00
27259
6379
5349
367
0.1327
0.0557
0.1407
Dcalc (g cmꢀ3
)
l (Mo Ka) (mmꢀ1
Crystal size (mm)
h Range (ꢁ)
)
0.15 · 0.15 · 0.08 0.20 · 0.10 · 0.05 0.30 · 0.15 · 0.10 0.15 · 0.12 · 0.10
3.03–26.00
17226
6298
5597
370
0.0800
0.0474
0.1340
1.093
3.18–26.00
10810
5309
4893
3.27–26.00
24286
5756
5756
3.98–26.00
19593
6613
4990
Number of reflections collected
Number of unique reflections
Number of observed reflectionsa
Number of parameters
Rint
343
372
381
0.0494
0.0432
0.1212
1.099
0.0639
0.0413
0.1043
1.012
0.1194
0.0685
0.2015
1.022
b
R1
wR2 (all data)b
Goodness-of-fit
1.056
Maximum and minimum heights in final
0.643, ꢀ0.844
1.180, ꢀ1.236
0.732, ꢀ1.232
5.276, ꢀ2.518
1.970, ꢀ1.513
ꢀ3
˚
difference Fourier synthesis (e A
)
a
I 6 2r(I).
P
P
P
P
2
1=2
b
R1 = ||Fo| ꢀ |Fc||/ |Fo|, wR2 ¼ ½ wðF 2o ꢀ F c2Þ = wF o4ꢁ
.
and Me2Te, respectively [d(Me2Se) = d(SeO2) + 1302.6;
d(Me2Te) = d(H6TeO6) + 712]. All spectra were recorded
unlocked.
The spectral simulations were carried out by using the
program Isotopomer [27].
groups (C–H = 0.99). In the final refinement the hydro-
gen atoms were riding with the carbon atom they were
bonded to. The isotropic thermal parameters of the aro-
matic hydrogen atoms were fixed at 1.2 times and the
methyl and methylene hydrogen atoms were fixed at 1.5
times to that of the corresponding carbon atom. The
scattering factors for the neutral atoms were those incor-
porated with the programs.
2.4. X-ray crystallography
Diffraction data for compounds 1–3, 3 Æ CH3OH, 4–7,
7 Æ 1/2CH2Cl2, and 8 were collected on a Nonius Kappa
CCD diffractometer at 120 K using graphite monochro-
The thienyl groups in 6–8 and the solvent molecules in
3 Æ CH3OH and 7 Æ 1/2CH2Cl2 turned out to be disordered.
In the refinement the disorder was taken into account, and
the site occupation factors of each disordered pair were
refined by constraining their sums to unity. Since the site
occupation factors and thermal parameters of the disor-
dered atoms correlate with each other, the thermal param-
eters of the corresponding pairs of atoms were restrained to
be equal.
˚
mated Mo Ka radiation (k = 0.71073 A). Crystal data
and details of the structure determinations are given in
Tables 1 and 2. The X-ray quality crystals of 1–4 and
6–8 were obtained by crystallization from CH2Cl2
layered with n-hexane. 3 Æ CH3OH was isolated upon
recrystallization of the crude product from toluene. The
X-ray-quality crystals of
5 and 7 Æ 1/2CH2Cl2 were
obtained from CH2Cl2 by slow evaporation of the
solvent.
3. Results and discussion
All structures were solved by direct methods using
SIR-92 [28] and refined using SHELXL-97 [29]. After the
full-matrix least-squares refinement of non-hydrogen
atoms with anisotropic thermal parameters, the hydrogen
atoms were placed in calculated positions in the aromatic
3.1. General
[M(EAr)2(dppe)] (M = Pd, Pt; E = Se, Te; Ar = phenyl,
2-thienyl) were synthesized by the reaction of [MCl2(dppe)]
with NaEPh or LiETh using a slight excess of the chalcogen-
olate. All complexes were analyzed by NMR spectroscopy
˚
rings (C–H = 0.95 A) and in the methyl and methylene

M. Risto et al. / Journal of Organometallic Chemistry 692 (2007) 2193–2204
2197
and structurally characterized in the solid state by single
crystal X-ray diffraction. All selenolato complexes are sta-
ble in air. Organyltellurolato palladium complexes, how-
ever, turned out to be moisture-sensitive and had to be
manipulated under a dry, inert atmosphere. The decompo-
sition of platinum complexes in the same conditions was
not observed.
The 77Se and 125Te NMR spectra of 1–8 exhibit single
resonances that appear as second-order multiplets due to
coupling to two chemically equivalent but magnetically
inequivalent phosphorus nuclei. In the case of the platinum
complexes, 195Pt satellites are also observed. They are
exemplified in Fig. 1 by comparison of the observed and
calculated 125Te resonances of the tellurolato complexes
3, 4, 7, and 8. The spectral simulations reproduce the
observed coupling patterns well. The intensity distributions
and the frequency separations of the multiplet components
are symmetric with respect to the assignment of the two
2JP–Te constants of different magnitudes either to cis- or
trans-coupling, and we cannot therefore assign unambigu-
3.2. NMR spectroscopy
The 31P{1H}, 77Se, 125Te, and 195Pt NMR spectroscopic
data of 1–8 are shown in Table 3. A single resonance in the
31P{1H} spectra of all complexes expectedly indicates that
the reactions produce only cis-[M(EAr2)(dppe)]. The chem-
2
2
ously the JP–Te or JP–Se coupling constants. However, it
has been deduced for related systems that the coupling is
larger to a phosphorus in trans-position and smaller to
the cis-phosphorus [32,33].
1
ical shifts and JPt–P coupling constants (where applicable)
are in agreement with those reported previously for
[Pd(SePh)2(dppe)] and [Pt(SePh)2(dppe)] (in C6D6 [24]; in
CDCl3 [22,23]), as well as for [Pd(TePh)2(dppe)] and
[Pt(TePh)2(dppe)] (in CDCl3 [24]).
The 77Se NMR spectroscopic data of 1, 2, 5, and 6 are
2
similar to those of [Pt(SePh)2(dppe)] (251 ppm; JSe–P
=
=
195Pt chemical shifts shown in Table 3 are consistent
with those of related [Pt(ER)2(dppe)] complexes {ER =
SePh (ꢀ4975 ppm [24]); SeCH2Ph (ꢀ4917 ppm [25]);
SeCH2CH2NMe2 (ꢀ4958 ppm [30]); Te(3-MeC5H3N)
(ꢀ5311 ppm [31]); Te(4-EtOC6H4) (ꢀ5310 ppm [24])}.
74 Hz, 11 Hz) and [Pd(SePh)2(dppe)] (202 ppm; JSe–P
2
80 Hz) [24]. The 77Se chemical shifts of cis-[Pt(SePh)2-
(PPh3)2], cis-[Pt(SeTh)2(PPh3)2], cis-[Pt(SetBu)2(PPh3)2],
and cis-[Pt(SenBu)2(PPh3)2] are 299 ppm [15], 187 ppm
[15], 254 ppm [19], and 136 ppm [19], respectively.
1
The 195Pt chemical shifts and JPt–P coupling constants of
No 125Te NMR spectroscopic data have previously been
reported for the tellurolato complexes of palladium and
platinum. The closest comparison can be made by consid-
ering trans ꢀ ½MðTeCORÞ2ðPR03Þ2ꢁ (M = Pd, Pt) [34]. The
125Te chemical shifts in the Pd complexes span a range of
362.1–443.8 ppm and those in the Pt complexes 329.4–
related complexes cis-[Pt(SePh)2(PPh3)2], cis-[Pt(SeTh)2-
(PPh3)2], cis-[Pt(SetBu)2(PPh3)2], and cis-[Pt(SenBu)2-
(PPh3)2] are ꢀ4904 ppm (2968 Hz) [15], ꢀ4863 ppm
(3041 Hz) [15], ꢀ4772 ppm (2928 Hz) [19], and ꢀ4914
ppm (2935 Hz) [19], respectively.
Table 3
31P{1H}, 77Se, 125Te, and 195Pt NMR data (d in ppm) for complexes 1–8
Compound
31P{1H} (d)a,b
77Se (d)c
125Te (d)c
195Pt (d)
[Pd(SePh)2(dppe)] (1)
53.5
248
2JP–Se 77 Hz, 7 Hz
–
–
2JP–P 14 Hz
0
[Pt(SePh)2(dppe)] (2)
47.1
1JPt–P 2951 Hz
204
1JPt–Se 186 Hz
–
ꢀ4960
1JPt–P 2951 Hz
1JPt–P 2890 Hz
1JPt–P 3006 Hz
1JPt–P 2901 Hz
2JSe–P 70 Hz
2JP–Se 77 Hz, ꢀ14 Hz
2
0
JP–P ¼ 10 Hz
[Pd(TePh)2(dppe)] (3)
[Pt(TePh)2(dppe)] (4)
48.2
46.8
–
–
297
177
2JP–Te 149 Hz, 38 Hz
–
2JP–P 30 Hz
0
1JPt–P 2896 Hz
2JTe–P 126 Hz
1JPt–Te 902 Hz
ꢀ5313
2JP–Te 130 Hz, 43 Hz
2JP–P 10 Hz
0
[Pd(SeTh)2(dppe)] (5)
[Pt(SeTh)2(dppe)] (6)
54.5
47.6
163
107
2JP–Se 63, 15 Hz
–
–
–
2JP–P 10 Hz
0
1JPt–P 3002 Hz
2JSe–P 61 Hz
1JPt–Se 216 Hz
ꢀ4947
2JP–Se 65 Hz, 15 Hz
2
0
JP–P ¼ 10 Hz
[Pd(TeTh)2(dppe)] (7)
[Pt(TeTh)2(dppe)] (8)
48.6
47.2
–
–
167
45
2JP–Te 88, 64 Hz
–
2JP–P 10 Hz
0
1JPt–P 2907 Hz
2JTe–P 94 Hz
1JPt–Te 1036 Hz
ꢀ5262
2JP–Te 96 Hz, 58 Hz
2JP–P 20 Hz
0
a
2
The satellites due to the smaller of the two JE–P coupling constants are obscured by the main signal.
b
The chalcogen satellites in the 31P spectra of the palladium complexes 1, 3, 5, and 7 only appear as shoulders at the side of the main resonance. While
the 2JP–E coupling seems to be of the same order of magnitude as those deduced for the larger coupling from the simulations of the chalcogen resonances, it
is not possible to estimate exact coupling constants.
c
The coupling constants have been obtained from the simulations of the second-order 77Se or 125Te multiplets.

2198
M. Risto et al. / Journal of Organometallic Chemistry 692 (2007) 2193–2204
31P
Th
Ph
Se
Pd → Pt
Th
Ph
Te
obs.
calc.
obs.
Th
Ph
Pd
Se → Te
Ph → Th
Th
Ph
Th
Ph
Pd
Pt
Pt
Se
Te
calc.
ppm
ppm
-2 -1
0
1
2
3
4
5
6
7
8
297
167
Δδ (ppm)
Th
Ph
Pd → Pt
Ph → Th
Pd → Pt
Ph → Th
Se →Te
Ph → Th
-100
77Se
125Te
195Pt
obs.
calc.
obs.
calc.
Pt
Pd
Th
Ph
Pt
Pd
Th
Ph
Te
Se
ppm
0
100
200
Δδ (ppm)
300
400
ppm
177
45
Fig. 1. The observed and simulated 125Te resonances in (a)
[Pd(TePh)2(dppe)], (b) [Pd(TeTh)2(dppe)], (c) [Pt(TePh)2(dppe)], and (d)
Fig. 2. The effect of varying the metal center (M = Pd, Pt), chalcogen
atom (E = Se, Te), and the aryl group (Ar = Ph, Th) on the 31P, 77Se,
125Te, and 195Pt chemical shifts in [M(EAr)2(dppe)] [dppe = 1,2-
bis(diphenylphosphino)ethane].
[Pt(TeTh)2(dppe)]. The simulations yielded the following coupling con-
2
0
stants: JP–P ¼ 30 Hz [Pd(TePh)2(dppe)], 10 Hz [Pd(TeTh)2(dppe)], 10 Hz
[Pt(TePh)2(dppe)], and 20 Hz [Pt(TeTh)2(dppe)]. For other relevant
coupling constants, see Table 3.
can be seen from Fig. 2 that other chemical shifts behave
in a similar fashion.
532.2 ppm (1JPt–Te: 681–812 Hz) [34]. These values, how-
ever, involve trans-isomers and only approximate agree-
ment should be expected with cis-isomers of 3, 4, 7, and
8. The 77Se resonances of the cis-isomers of various seleno-
lato platinum complexes are found upfield from those of
It has been known for a long time that many analogous
tellurium and selenium compounds show a constant ratio
of ca. 1.6 in the 125Te and 77Se chemical shifts [36]. While
in the case of the Pt(II) and Pd(II) complexes, the analo-
gous telluroether and selenoether complexes also show a
similar ratio of 1.8 [37,38], it is interesting to note that in
the case of current dppe complexes 1–8, the d(125Te):d(77Se)
ratios between the analogous species are significantly smal-
ler. It can be seen from Table 3 that the d(125Te):d(77Se)
ratio is 1.2 for 3 and 1 and 1.0 for 7 and 5. Even smaller
ratios of 0.9 and 0.4 are observed for the two pairs of
platinum complexes 4–2 and 8–6, respectively. The
d(125Te):d(77Se) ratio for the tellurocarboxylato and seleno-
carboxylato trans ꢀ ½MðECORÞ2ðPR03Þ2ꢁ (M = Pt, Pd; E =
Te, Se) is of the same order of magnitude (ca. 1.1–1.2)
[34,39].
1
the trans-isomers. The JSe–Pt coupling constants of the
cis-isomers are larger than those of the trans-isomers,
These trends are exemplified by cis- and trans-
[Pt(SePh)2(PPh3)2] (299 and 176 ppm, respectively) [15].
The 2JP–Te coupling constants of 3, 4, 7, and 8 can be com-
pared with that of [PtCl{Te(C6H4OCH2CH3-4)}(PPh3)2]
[35].
The trends in the chemical shifts are shown in Fig. 2. It
is interesting to note that the relative changes in the chem-
ical shifts when varying the metal, chalcogen, or the
organic substituent in the complexes seem to be indepen-
dent on changes in other parts of the molecule. For
instance, the difference in the 31P chemical shifts is
6.4 ppm between [Pd(SePh)2(dppe)] and [Pt(SePh)2(dppe)],
and 6.9 ppm between [Pd(SeTh)2(dppe)] and [Pt(SeTh)2-
(dppe)] with the resonance of the platinum complex
appearing upfield. Similarly, the difference in the 125Te
chemical shifts is 120 ppm between [Pd(TePh)2(dppe)] and
[Pt(TePh)2(dppe)], and 122 ppm between [Pd(TeTh)2
(dppe)] and [Pt(TeTh)2(dppe)] with the 125Te resonance of
the platinum complex appearing upfield in both cases. It
3.3. Crystal structures
The chalcogenolato complexes 1–8 can be subdivided
into five isomorphic series: [Pd(SePh)2(dppe)] (1) and
[Pt(SePh)2(dppe)] (2), [Pd(TePh)2(dppe)] (3) and [Pt(TePh)2-
(dppe)] (4), [Pd(SeTh)2(dppe)] (5), [Pt(SeTh)2(dppe)] (6)
and [Pd(TeTh)2(dppe)] (7), and [Pt(TeTh)2(dppe)] (8).
Their molecular structures indicating the numbering of
atoms are shown in Figs. 3–5. In addition, two complexes

M. Risto et al. / Journal of Organometallic Chemistry 692 (2007) 2193–2204
2199
Se(4)
Se(3)
Pt(2)
P(1)
Te(2)
P(4)
P(3)
Pd(1)
Te(1)
P(2)
Se(1)
Se(2)
Fig. 4. The molecular structure of isomorphic [M(TePh2)(dppe)] [M = Pd
(3), Pt (4)] complex indicating the numbering of atoms. The thermal
ellipsoids have been drawn at 50% probability level. The structure in the
figure is that of 3.
P(2)
Pt(1)
P(1)
n
˚
˚
˚
2.476(1) A] [40], trans-[Pd(SePh)2(P Bu3)2] [2.4609(4) A]
[41] and trans-[Pd(4-MeC6H4COSe)2(PEt3)2] [2.456(1) A]
[39], as well as with the Pt–Se bond lengths in
[Pt(SePh)2(dppm)] [dppm = bis(diphenylphosphino)meth-
˚
ane] [2.4340(9), 2.461(1) A] [42], [Pt(SeCOPh)2(dppp)]
[dppp = 1,3-bis(diphenylphosphino)propane] [2.48218(11),
Fig. 3. The molecular structure of isomorphic [M(SePh)2(dppe)] [M = Pd
(1), Pt (2)] indicating the numbering of atoms. The thermal ellipsoids have
been drawn at 50% probability level. The structure in the figure is that of
2.
˚
˚
2.4613(10) A] [43], and 2.4506(5)–2.5119(9) A in cis- and
trans-[Pt(SeAr)2(PPh3)2] {Ar = Fu (2-furyl, C4H3O), Th
(2-thienyl, C4H3S), Ph} [15].
The Pd–Te bond lengths in corresponding tellurolato
˚
complexes show a range of 2.5871(7)–2.6704(8) A in 3,
crystallize also with the solvent of crystallization:
[Pd(TePh)2(dppe)] Æ CH3OH (3 Æ CH3OH) and [Pd(TeTh)2-
(dppe)] Æ 1/2CH2Cl2 (7 Æ 1/2CH2Cl2). Their crystal struc-
tures indicating the numbering of atoms as well as the
interaction with the disordered solvent molecules are
shown in Fig. 6. Selected bond parameters of 1–4 are
shown in Table 4 and those of 5–8 are shown in Table 5.
The lattice of each complex is composed of discrete
molecular units with the metal atom exhibiting an approx-
imate square-planar coordination [RM = 359.97–360.52ꢁ
(M = Pd, Pt)], though the individual bond angles are sig-
nificantly deviated from the ideal value of 90ꢁ.
3 Æ CH3OH, 7, and 7 Æ 1/2CH2Cl2. They are consistent with
the Pd–Te bond length of 2.6380(8) A of the terminal thie-
˚
nyl tellurolato ligand in hexanuclear [Pd6(Te4)(TeTh)4-
(PPh3)6] [16], but they are slightly longer than those in
˚
[PdCl{Te(3-MeC5H3N)}(PPh3)] [2.5606(8) A] [31], [PdCl-
(TeCH2CH2NMe2)(PnPr3)] [2.5095(8) A], and [PdCl-
˚
˚
(TeCH2CH2NMe2)(PMePh2)] [2.5161(6) A] [44]. It reflects
the stronger trans-influence of phosphorus compared to
that of chlorine.
The Pt–Te bonds in 4 and 8 show the length range of
˚
2.6053(6)–2.6594(9) A. The bonds are in agreement with
˚
those of cis-[Pt(1,2-Te2C6H4)(PPh3)2] [2.586(1) A] [45],
As shown in Tables 4 and 5, the Pd–Se bonds in 1 and 5
trans-[Pt(4-MeC6H4COTe)2(PEt3)2]
[2.592(1)
and
span a range of 2.4350(7)–2.4828(7) A, and the Pt–Se bond
2.632(2) A] [34], and cis-[PtCl{Te(2,4,6-tBu3C6H2)}-
˚
˚
˚
˚
lengths in 2 and 6 are 2.442(1)–2.511(1) A. All these bonds
(PPh3)2] [2.614(1) A] [46].
correspond to single bond lengths and are in agreement
The respective Pd–P and Pt–P bond distances of
2.265(2)–2.295(2) A and 2.247(2)–2.270(2) A are quite nor-
mal for phosphine–metal coordination. They agree well
˚
˚
with the Pd–Se bond lengths in [Pd(SePh)2(dppe)] Æ C6H6
˚
[2.444(1), 2.480(1) A] [24], [Pd(SeCN)2(dppe)] [2.478(1),

2200
M. Risto et al. / Journal of Organometallic Chemistry 692 (2007) 2193–2204
˚
MeC5H3N)}(PPh3)] [2.242(2) A] [31], [PdCl(TeCH2CH2N-
n
˚
Me2)(P Pr3)] [2.209(1) A] [44] and [PdCl(TeCH2CH2N-
˚
Me2)(PMePh2)] [2.230(1) A] [44].
It is interesting to note that in each complex 1–8, one of
the E–M–E–C(aryl) torsional angles shows a range of
169.0(2)–179.9(3)ꢁ (see Tables 4 and 5). Therefore, the E–
C(aryl) bond of one of the chalcogenolato ligands lies
approximately on the square-planar M(E2)(P2) coordina-
tion plane with that of the other chalcogenolato ligand
deviating from coplanarity. The angles between the rele-
vant least-squares planes are shown in Fig. 7. The angle
between the E–C(aryl) bond of the second chalcogenolato
ligand and the M(E2)(P2) coordination plane is dependent
on the E–M–E bond angle. When the bond angle is small,
the E–C bond is approximately perpendicular to the coor-
dination plane, but as the bond angle increases, also this E–
C bond approaches coplanarity.
P(1)
P(2)
Pd(1)
S(2)
Se(1)
Se(2)
S(1)
A second trend can also be seen from Fig. 7. When the
E–C(aryl) bond is coplanar with the M(E2)(P2) plane, the
corresponding M–E bond of the M–E–Ar moiety is
approximately perpendicular to the plane of the aromatic
ring. When the angle between the E–C bond and the
M(E2)(P2) coordination plane is larger, the angle between
the M–E bond and the plane of the aromatic ring
decreases. When the E–C bond is perpendicular to the
coordination plane, the M–E bond is almost coplanar with
the aromatic ring. It has previously been observed that
there are two possible stable conformations in diarylditellu-
rides ArEEAr: one in which the E–E bond is perpendicular
to both aromatic rings, and the other in which the aromatic
rings are coplanar with the E–E bonds [48].
P(1)
P(2)
Pd(1)
S(11A)
Te(2)
Te(1)
S(21A)
4. Conclusions
A series of mononuclear [M(EAr)2(dppe)] [M = Pd, Pt;
E = Se, Te; Ar = phenyl, 2-thienyl; dppe = 1,2-bis(diph-
enylphosphino)ethane] complexes has been prepared in
good yields by the reactions of [MCl2(dppe)] with ArEꢀ.
The trends in the structural and NMR spectroscopic prop-
erties of the complexes have been explored as a function of
the identity of the metal center, chalcogen atom, and aro-
matic ring. In particular, we report in this contribution
crystal structures of a number of aryltellurolato-palladium
and -platinum complexes for which the existing solid state
structural information is virtually non-existent.
The use of a chelating ligand forces the formation of
mononuclear cis-chalcogenolato complexes. Those that
have been prepared in this work crystallize in five isomor-
phic groups: (1) [Pd(SePh)2(dppe)] and [Pt(SePh)2(dppe)],
(2) [Pd(TePh)2(dppe)] and [Pt(TePh)2(dppe)], (3)
[Pd(SeTh)2(dppe)], (4) [Pt(SeTh)2(dppe)] and [Pd(TeTh)2-
(dppe)], and (5) [Pt(TePh)2(dppe)]. In addition, solvated
Pt(1)
P(2)
P(1)
Te(1)
Te(2)
S(21A)
S(11A)
Fig. 5. The molecular structures of (a) [Pd(SeTh)2(dppe)] (5), (b)
isomorphic [Pt(SeTh)2(dppe)] (6) and [Pd(TeTh)2(dppe)] (7), and (c)
[Pt(TeTh)2(dppe)] (8) indicating the numbering of atoms. The thermal
ellipsoids have been drawn at 50% probability level.
[Pd(TePh)2(dppe)] Æ CH3OH
and
[Pd(TeTh)2(dppe)] Æ
1/2CH2Cl2 could be isolated and structurally characterized.
The arylchalcogenolato ligands assume varying orienta-
tions with respect to the square-planar coordination sphere
around the metal center. The chalcogen–carbon bond of
˚
˚
with those in [Pt3Te2(Th)(PPh3)5]Cl [2.266(7)–2.296(7) A]
[16] and [Pd2(l2-Te)2(dppe)2] [2.286(2) and 2.287(2) A]
[47], but are slightly longer than those in [PdCl{Te(3-

M. Risto et al. / Journal of Organometallic Chemistry 692 (2007) 2193–2204
2201
b
a
Te(1)
c
Te(2)
Pd(1)
P(1)
P(2)
b
c
Te(1)
a
Pd(1)
Te(2)
P(2)
P(1)
Fig. 6. The molecular structures of (a) [Pd(TeTh)2(dppe)] Æ 1/2CH2Cl2 (7 Æ 1/2CH2Cl2) and (b) [Pd(TePh)2(dppe)] Æ CH3OH (3 Æ CH3OH) indicating the
numbering of atoms. In both complexes the solvent is disordered (s.o.f. 0.5). The close contacts between the disordered solvent molecules and the
complexes are also indicated in the figures. The thermal ellipsoids have been drawn at 50% probability level.

2202
M. Risto et al. / Journal of Organometallic Chemistry 692 (2007) 2193–2204
Table 4
˚
Selected bond lengths (A) and angles (ꢁ) of complexes 1–4
1
2
3
3 Æ CH3OH
4
M(1)–E(1)/M(2)–E(3)
M(1)–E(2)/M(2)–E(4)
M(1)–P(1)/M(2)–P(3)
M(1)–P(2)/M(2)–P(4)
E(1)–M(1)–E(2)
E(1)–M(1)–P(1)
E(1)–M(1)–P(2)
E(2)–M(1)–P(1)
E(2)–M(1)–P(2)
2.4350(7)/2.4655(7)
2.4828(7)/2.4522(8)
2.274(1)/2.270(1)
2.265(1)/2.277(1)
82.46(3)
173.05(3)
100.43(4)
91.27(4)
2.442(1)/2.474(1)
2.492(1)/2.459(1)
2.252(2)/2.254(2)
2.247(2)/2.250(2)
81.59(4)
172.24(6)
101.08(6)
91.34(6)
2.6361(9)
2.5933(8)
2.279(2)
2.271(2)
89.97(4)
171.58(5)
86.15(6)
97.88(6)
175.08(5)
86.16(7)
2.5871(7)
2.6328(8)
2.274(2)
2.278(2)
89.42(3)
172.06(4)
99.83(5)
85.87(5)
169.74(4)
85.40(6)
2.6465(7)
2.6053(6)
2.251(1)
2.249(1)
89.32(3)
172.03(3)
86.44(4)
97.90(4)
174.77(3)
86.52(5)
177.11(3)
85.85(5)
177.28(6)
86.02(8)
P(1)–M(1)–P(2)
E(3)–M(2)–E(4)
91.97(2)
90.76(3)
E(3)–M(2)–P(3)
E(3)–M(2)–P(4)
166.71(3)
84.88(4)
167.40(6)
85.37(6)
E(4)–M(2)–P(3)
98.09(3)
98.39(6)
E(4)–M(2)–P(4)
P(3)–M(2)–P(4)
174.07(3)
85.82(4)
174.38(6)
86.06(7)
E(2)–M(1)–E(1)–C(11)
E(1)–M(1)–E(2)–C(21)
E(4)–M(2)–E(3)–C(31)
E(3)–M(2)–E(4)–C(41)
M(1)–E(1)–C(11)–C(12)
M(1)–E(1)–C(11)–C(16)
M(1)–E(2)–C(21)–C(22)
M(1)–E(2)–C(21)–C(26)
M(2)–E(3)–C(31)–C(32)
M(2)–E(3)–C(31)–C(36)
M(2)–E(4)–C(41)–C(42)
M(2)–E(4)–C(41)–C(46)
ꢀ179.3(2)
ꢀ179.7(3)
22.6(2)
169.0(2)
ꢀ169.8(2)
ꢀ21.6(2)
21.7(1)
169.2(2)
ꢀ86.6(1)
ꢀ85.4(2)
ꢀ24.9(2)
ꢀ26.2(3)
ꢀ175.9(2)
ꢀ86.5(4)
ꢀ177.5(3)
ꢀ84.7(8)
ꢀ105.7(5)
75.7(6)
ꢀ106.3(5)
83.0(5)
ꢀ106.7(4)
75.1(4)
102.9(3)
103.2(7)
ꢀ173.4(4)
ꢀ174.1(6)
ꢀ83.0(6)
ꢀ76.9(5)
ꢀ81.9(4)
9.5(4)
8.2(7)
107.4(6)
106.0(6)
107.7(4)
ꢀ49.2(4)
ꢀ48.6(8)
134.6(4)
134.4(6)
ꢀ77.4(4)
ꢀ75.7(8)
107.9(3)
109.0(6)
Table 5
˚
Selected bond lengths (A) and angles (ꢁ) of complexes 5–8
5
6
7
7 Æ 1/2 CH2Cl2
8
M(1)–E(1)
M(1)–E(2)
M(1)–P(1)
M(1)–P(2)
2.480(1)
2.455(1)
2.274(2)
2.265(2)
90.15(3)
168.30(6)
83.93(6)
100.29(6)
173.60(6)
85.84(7)
ꢀ33.0(3)
179.9(3)
90.5(7)
2.451(1)
2.511(1)
2.263(2)
2.270(2)
80.88(5)
173.52(7)
100.33(7)
93.05(7)
178.53(9)
85.71(8)
ꢀ171.9(2)
85.7(4)
2.5871(8)
2.6704(8)
2.292(2)
2.295(2)
79.56(4)
173.67(5)
100.10(6)
94.30(5)
178.76(7)
86.01(7)
2.619(1)
2.609(1)
2.292(3)
2.283(3)
89.71(3)
170.61(9)
85.10(8)
99.48(8)
173.53(8)
85.9(1)
2.6594(9)
2.607(1)
2.267(2)
2.257(2)
82.09(3)
170.65(6)
90.08(6)
101.12(6)
172.16(6)
86.69(8)
74.0(1)
E(1)–M(1)–E(2)
E(1)–M(1)–P(1)
E(1)–M(1)–P(2)
E(2)–M(1)–P(1)
E(2)–M(1)–P(2)
P(1)–M(1)–P(2)
E(2)–M(1)–E(1)–C(11)
E(1)–M(1)–E(2)–C(21)
M(1)–E(1)–C(11)–C(12)
M(1)–E(1)–C(11)–S(11)
M(1)–E(2)–C(21)–C(22)
M(1)–E(2)–C(21)–S(21)
ꢀ174.0(2)
9.8(4)
86.8(2)
172.2(3)
ꢀ96.5(9)
91.2(6)
90.4(9)
ꢀ102.8(6)
ꢀ172.4(2)
91.9(2)
93.9(5)
ꢀ6.7(1)
ꢀ91.8(4)
ꢀ92.4(8)
99.5(5)
ꢀ100.7(5)
ꢀ37.4(1)
137.4(8)
ꢀ100.5(4)
ꢀ43.3(6)
134.8(4)
173.5(2)
ꢀ109.2(6)
82.6(6)
one of the chalcogenolato ligands is almost coplanar with
the M(E2)(P2) plane in each complex. The orientation of
the other ligand, however, depends on the E–M–E bond
angle. The orientation of the aryl ring with respect to the
M–E bond of the ligand also depends on the angle between
the corresponding E–C bond and the M(E2)(P2) plane.
The NMR spectroscopic and X-ray crystallographic
information indicates the formation of only cis-[M(EAr)2-
(dppe)] complexes. The 77Se or 125Te resonances in 1–8
appear as second-order multiplets. Spectral simulation
has yielded all relevant coupling constants. The trends in
the 31P, 77Se, 125Te, and 195Pt chemical shifts expectedly
depend on the nature of metal, chalcogen, and aryl group.
We note that each trend can be considered independently
of other factors.
Supplementary material
CCDC 631144, 631145, 631146, 631147, 631148,
631149, 631150, 631151, 631152 and 631153 contain the

M. Risto et al. / Journal of Organometallic Chemistry 692 (2007) 2193–2204
[9] R. Zanella, R. Ros, M. Graziani, Inorg. Chem. 12 (1973) 2736.
2203
Φ (deg)
[10] I. Nakanishi, S. Tanaka, K. Matsumoto, S. Ooi, Acta Crystallogr.
C50 (1994) 58.
100
90
80
70
60
50
40
30
20
10
´
[11] M.S. Hannu-Kuure, K. Paldan, R. Oilunkaniemi, R.S. Laitinen, M.
´
Ahlgren, J. Organomet. Chem. 667 (2003) 38.
´
[12] M.S. Hannu-Kuure, R. Oilunkaniemi, R.S. Laitinen, M. Ahlgren,
Acta Crystallogr. E60 (2004) m214.
[13] A. Wagner, M.S. Hannu-Kuure, R. Oilunkaniemi, R.S. Laitinen,
Acta Crystallogr. E61 (2005) m2198.
´
[14] M.S. Hannu, R. Oilunkaniemi, R.S. Laitinen, M. Ahlgren, Inorg.
Chem. Commun. 3 (2000) 397.
[15] M.S. Hannu-Kuure, J. Komulainen, R. Oilunkaniemi, R.S.
´
Laitinen, R. Suontamo, M. Ahlgren, J. Organomet. Chem. 666
(2003) 111.
´
[16] R. Oilunkaniemi, R.S. Laitinen, M. Ahlgren, J. Organomet. Chem.
0
595 (2000) 232.
75
80
85
90
95
[17] L.-Y. Chia, W.R. McWhinnie, J. Organomet. Chem. 148 (1978)
165.
< E-M-E (deg)
[18] R. Oilunkaniemi, R.S. Laitinen, J. Pursiainen, M. Ahlgre´n, Phos-
phorus, Sulfur, Silicon 136–138 (1998) 577.
[19] M.S. Hannu-Kuure, A. Wagner, T. Bajorek, R. Oilunkaniemi, R.S.
The angle between the E-C(aryl) bond and the square-planar M(E2)(P2) least-
squaresplane in case of the two chalcogenolato ligands
´
Laitinen, M. Ahlgren, Main Group Chem. 4 (2005) 49.
[20] N.V. Kirij, W. Tyrra, I. Pantenburg, D. Naumann, H. Scherer,
D. Naumann, Y.L. Yagupolskii, J. Organomet. Chem. 691
(2006) 2679.
The angle between the M-E bond and the least-squares plane of the aromatic ring in
the corresponding arylchalcogenolato ligands indicated in gray.
[21] (a) V.K. Jain, S. Kannan, E.R.T. Tiekink, J. Chem. Res. (S) (1994)
85;
Fig. 7. The dependence of the angle between the least-squares planes
containing the atoms M–E–C(aryl) (M = Pd, Pt; E = Se, Te; aryl = Ph, Th)
and the square-planar coordination plane M(E2)(P2) on the E–M–E bond
angle in 1–8. One E–C bond in each complex is approximately coplanar
with the coordination plane (indicated with a gray square). The angle of the
second E–C bond (indicated with a gray triangle) is more strongly
dependent on the E–M–E bond angle. The open square and open triangle
indicate the angle between the E–C bond and the aromatic rings. The open
square defines the bond that is coplanar with coordination plane and the
open triangle defines the E–C bond of the other chalcogenolato ligand.
(b) V.K. Jain, S. Kannan, E.R.T. Tiekink, J. Chem. Res. (M) (1994)
0501.
[22] S.K. Gupta, B.L. Khandelwal, Ind. J. Chem. 29A (1990) 977.
[23] C. Xu, J.W. Siria, G.K. Anderson, Inorg. Chim. Acta 206 (1993)
123.
[24] A. Singhal, V.K. Jain, B. Varghese, E.R.T. Tiekink, Inorg. Chim.
Acta 285 (1999) 190.
[25] S. Dey, V.K. Jain, B. Varghese, J. Organomet. Chem. 623 (2001)
48.
[26] T. Appleton, M.A. Bennett, I.B. Tomkins, J. Chem. Soc., Dalton
Trans. (1976) 439.
[27] D.P. Santry, H.P.A. Mercier, G.J. Schrobilgen, ISOTOPOMER A
Multi-NMR Simulation Program, version 3.02NTF, Snowbird Soft-
ware Inc., Hamilton, Ont., Canada, 2000.
[28] A. Altomare, G. Cascarano, C. Giacovazzo, A. Gualardi, J. Appl.
Cryst. 26 (1993) 343.
[29] G.M. Sheldrick, SHELXL-97. Program for Crystal Structure Refine-
ment, University of Go¨ttingen, 1997.
supplementary crystallographic data for 1–8, 3 Æ CH3OH,
and 7 Æ 1/2 CH2Cl2. These data can be obtained free of
charge via http://www.ccdc.cam.ac.uk/conts/retrieving.
html, or from the Cambridge Crystallographic Data Cen-
tre, 12 Union Road, Cambridge CB2 1EZ, UK; fax:
(+44) 1223-336-033; or e-mail: deposit@ccdc.cam.ac.uk.
[30] S. Dey, V.K. Jain, A. Knoedler, W. Klaim, S. Zalis, Eur. J. Inorg.
Chem. (2001) 2965.
Acknowledgement
[31] S. Dey, V.K. Jain, J. Singh, V. Trehan, K.K. Bhasin, B. Varghese,
Eur. J. Inorg. Chem. (2003) 744.
[32] S. Ford, C.P. Morley, M. Di Vaira, New J. Chem. 23 (1999) 811.
[33] S. Ford, C.P. Morley, M. Di Vaira, Inorg. Chem. 43 (2004) 7101.
[34] S. Kato, O. Niyomura, Y. Kawahara, T. Kanda, J. Chem. Soc.,
Dalton Trans. (1999) 1677.
Financial support from Academy of Finland is grate-
fully acknowledged.
References
[35] B. Khandelwal, K. Kundu, S.K. Gupta, Inorg. Chim. Acta 148
(1988) 255.
[36] H.C.E. McFarlene, W. McFarlene, J. Chem. Soc., Dalton Trans.
(1973) 2416.
[37] T. Kemmitt, W. Levason, M. Webster, Inorg. Chem. 28 (1989)
692.
[1] V.P. Ananikov, M.A. Kabeshov, I.P. Beletskaya, G.G. Aleksandrov,
I.L. Eremenko, J. Organomet. Chem. 687 (2003) 451.
[2] V.P. Ananikov, I.P. Beletskaya, G.G. Aleksandrov, I.L. Eremenko,
Organometallics 22 (2003) 1414.
[3] V.P. Ananikov, I.P. Beletskaya, Doklady Chem. 389 (2003) 81.
[4] V.P. Ananikov, N.V. Orlov, I.P. Beletskaya, Russ. Chem. Bull. Int.
Ed. 54 (2005) 576.
[5] V.P. Ananikov, I.P. Beletskaya, Org. Biomol. Chem. 2 (2004) 284.
[6] V.P. Ananikov, M.A. Kabeshov, I.P. Beletskaya, V.N. Khrustalev,
M.Y. Antipin, Organometallics 24 (2005) 1275.
´
[38] R. Oilunkaniemi, J. Komulainen, R.S. Laitinen, M. Ahlgren, J.
Pursiainen, J. Organomet. Chem. 129 (1998) 521.
[39] Y. Kawahara, S. Kato, T. Kanda, T. Murai, K. Miki, J. Chem. Soc.,
Dalton Trans. (1996) 79.
[40] C.A. Grygon, W.C. Fultz, A.L. Rheingold, J.L. Burmeister, Inorg.
Chim. Acta 144 (1988) 31.
´
[7] R. Oilunkaniemi, R.S. Laitinen, M. Ahlgren, J. Organomet. Chem.
587 (1999) 200.
[41] E.C. Alyea, G. Ferguson, S. Kannan, Polyhedron 17 (1998) 2231.
[42] V.K. Jain, S. Kannan, R.J. Butcher, J.P. Jasinski, J. Chem. Soc.,
Dalton Trans. (1993) 1509.
´
[8] R. Oilunkaniemi, R.S. Laitinen, M. Ahlgren, J. Organomet. Chem.
623 (2001) 168.

2204
M. Risto et al. / Journal of Organometallic Chemistry 692 (2007) 2193–2204
[43] L.B. Kumbhare, V.K. Jain, B. Varghese, Inorg. Chim. Acta 359
(2006) 409.
[46] P.J. Bonasia, J. Arnold, J. Organomet. Chem. 449 (1993) 147.
[47] C. Nishitani, T. Shizuka, K. Matsumoto, S. Okeya, H. Kimoto,
Inorg. Chem. Commun. 1 (1998) 325.
´ ˇ
[44] S. Dey, V.K. Jain, A. Kno¨dler, A. Klein, W. Kaim, S. Zalis, Inorg.
´
Chem. 41 (2002) 2864.
[48] R. Oilunkaniemi, R.S. Laitinen, M. Ahlgren, Z. Naturforsch. 55b
[45] D.M. Giolando, T.B. Rauchfuss, A.L. Rheingold, Inorg. Chem. 26
(1987) 1636.
(2000) 361, and references therein.