Versatile coordination chemistry of rhodium complexes containing the bis(trimethylsilylmethyl)tellane ligand

Article abstract of DOI:10.1016/j.jorganchem.2009.02.001

When RhCl₃ · 3H₂O was treated with an excess of Te(CH₂SiMe₃)_2, a mononuclear mer-[RhCl₃{Te(CH₂SiMe₃)₂}₃] (1) was observed as the main product. By

Full text of DOI:10.1016/j.jorganchem.2009.02.001

Journal of Organometallic Chemistry 694 (2009) 2053–2060
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Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Versatile coordination chemistry of rhodium complexes containing
the bis(trimethylsilylmethyl)tellane ligand
*
*
Ludmila Vigo, Merja J. Poropudas, Pekka Salin, Raija Oilunkaniemi , Risto S. Laitinen
Department of Chemistry, University of Oulu, P.O. Box 3000, FI-90014 Oulu, Finland
a r t i c l e i n f o
a b s t r a c t
Article history:
When RhCl3 ꢀ 3H2O was treated with an excess of Te(CH2SiMe3)2, a mononuclear mer-[RhCl3{Te(CH2-
SiMe3)2}3] (1) was observed as the main product. By reducing the metal-to-ligand molar ratio, dinuclear
Received 10 January 2009
Received in revised form 30 January 2009
Accepted 3 February 2009
Available online 13 February 2009
[Rh2(
ligand ratio resulted in the formation of [Rh2(
of mer-[RhCl3(SMePh)3] (4) with two equivalents of Te(CH2SiMe3)2 affords
l
-Cl)2Cl4{Te(CH2SiMe3)2}4] (2) was obtained in addition to 1. Further reduction of the metal-to-
-Cl)2Cl4(OHCH2CH3){Te(CH2SiMe3)2}3] (3). The treatment
mixture of mer-
l
a
[RhCl3{Te(CH2SiMe3)2}3] (1) and mer-[RhCl3{Te(CH2SiMe3)2}2(SMePh)] (5). All complexes 1–4 and
5 ꢀ ½EtOH were characterized by X-ray crystallography and 125Te NMR spectroscopy, where appropriate.
The definite assignment of the 125Te chemical shifts enabled a plausible discussion of the assignment of
some unknown resonances that were observed in the NMR spectra.
Keywords:
Bis(trimethylsilylmethyl)tellane
Mononuclear rhodium complexes
Dinuclear rhodium complexes
Molecular Structure
Ó 2009 Elsevier B.V. All rights reserved.
X-ray diffraction
NMR spectroscopy
1. Introduction
and [Rh2(l-Cl)2Cl4(OHCH2CH3){Te(CH2SiMe3)2}3] (3). We also de-
scribe the ligand substitution reaction in mer-[RhCl3(SMePh)3] (4)
by Te(CH2SiMe3)2 that leads to the formation of 1 and hybrid
mer-[RhCl3{Te(CH2SiMe3)2}2(SMePh)] (5). We have recently re-
ported that the ligand substitution of SRPh (R = Ph, Me) in
[MCl2(SRPh)2] (M = Pt, Pd) by Te(CH2SiMe3)2 affords a mixture of
complexes containing [MCl2(SRPh)2], [MCl2(SRPh){Te(CH2SiMe3)2}],
and [MCl2{Te(CH2SiMe3)2}2] [17].
There is only little information on the chemistry of rhodium
complexes containing telluroether ligands (for some selected re-
views, see Refs. [1–5]). One of the first examples was the reported
synthesis of [RhCl3(TePh2)3] from RhCl3 and diphenyl telluride [6],
but no structural information was given. More recently, the exis-
tence of both mer- and fac-isomers of [RhCl3L3] (L = 1,3-dihydro-
benzo[c]tellurophene, tetrahydrotellurophene) complexes in
solution was inferred based on NMR spectroscopic information
[7,8].
2. Experimental
Of the few known crystal structures of mononuclear rhodium
complexes that contain telluroether ligands [9–13], [RhCp*L][PF6]2
{L = MeS(CH2)3Te((CH2)3SMe)} is of special interest, since L acts as
a tridentate ligand with one Te and two S donor atoms [13]. To our
knowledge, no crystal structures of such hybrid rhodium com-
plexes containing discrete thioether and telluroether ligands have
hitherto been reported.
2.1. General
RhCl3 ꢀ 3H2O (Aldrich), SMePh (Aldrich), ethanol (Altia), diethyl
ether (Lab-Scan), and dichloromethane (Lab-Scan) were used as
purchased and without further purification. Te(CH2SiMe3)2 was
prepared using the method described by Gysling et al. [14].
Bis(trimethylsilylmethyl)tellane ligand forms complexes with
palladium(II), platinum(II), and ruthenium(II) centres that exhibit
interesting stereochemical features [14–16]. In this paper, we are
concerned with the reaction of Te(CH2SiMe3)2 and RhCl3 ꢀ 3H2O.
We discuss the formation and structural characterization of mer-
2.2. NMR spectroscopy
13C{1H} and 125Te NMR spectra were recorded on a Bruker
DPX400 spectrometer operating at 100.61 MHz and 126.28 MHz,
respectively. The typical respective spectral widths were
[RhCl3{Te(CH2SiMe3)2}3] (1), [Rh2(l-Cl)2Cl4{Te(CH2SiMe3)2}4] (2),
24.04 kHz and 126.58 kHz. The pulse widths were 11.00 ls and
10.00 l
s, respectively. 13C{1H} pulse delay was 6.00 s and that for
* Corresponding authors. Tel.: +358
8 5531686; fax: +358 8 5531603
125Te was 1.60 s. 13C{1H} accumulations contained ca. 1000 tran-
sients and those for 125Te 40000 transients. Tetramethylsilane
was used as an internal standard for 13C{1H}, and a saturated
(R. Oilunkaniemi), tel.: +358 8 5531611; fax: +358 8 5531603 (R.S. Laitinen).
E-mail addresses: raija.oilunkaniemi@oulu.fi (R. Oilunkaniemi), risto.laitinen@
oulu.fi (R.S. Laitinen).
0022-328X/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2009.02.001

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L. Vigo et al. / Journal of Organometallic Chemistry 694 (2009) 2053–2060
Table 1
Crystal data and details of the structure determinations of mer-[RhCl3{Te(CH2SiMe3)2}3] (1), [Rh2(
l
-Cl)2Cl4{Te(CH2SiMe3)2}4] (2), [Rh2(l-Cl)2Cl4(OHCH2CH3){Te(CH2SiMe3)2}3]
(3), mer-[RhCl3(SMePh)3] (4), and mer-[RhCl3{Te(CH2SiMe3)2}2(SMePh)] ꢀ ½C2H5OH (5 ꢀ ½EtOH).
1
2
3
4
5 ꢀ ½EtOH
Empirical formula
Relative molecular mass
Crystal system
Space group
a (Å)
C24H66Cl3RhSi6Te3
1115.37
Monoclinic
P21/n
14.722(3)
18.908(4)
17.334(4)
98.25(3)
4775(2)
4
C32H88Cl6Rh2Si8Te4
1626.66
Monoclinic
P21/c
20.311(4)
14.151(3)
23.292(5)
103.97(3)
6496(2)
4
C26H72Cl6ORh2Si6Te3
1370.70
Monoclinic
P21/c
11.276(2)
21.972(4)
21.429(4)
97.83(3)
5260(2)
4
C21H24Cl3RhS3
C24H55Cl3O0.50RhSSi4Te2
960.56
Monoclinic
P21/c
16.871(3)
19.055(4)
13.202(3)
100.29(3)
4176(1)
4
581.84
Monoclinic
P21/c
15.679(3)
10.278(2)
15.812(3)
111.92(3)
2363.9(8)
4
b (Å)
c (Å)
b (°)
V (Å3)
Z
F(000)
2184
1.551
2.486
3168
1.663
2.684
2672
1.731
2.720
1176
1.635
1.333
1900
1.528
2.150
Dcalc. (g cmꢁ3
)
l(Mo K
a
) (mmꢁ1
)
Crystal size (mm)
h range (°)
No. of reflections collected
No. of unique reflections
No. of observed reflectionsa
No. of parameters/restraints
0.40 ꢂ 0.20 ꢂ 0.10
3.00–26.00
43539
9250
7221
0.30 ꢂ 0.20 ꢂ 0.10
3.02–26.00
64473
12713
9481
0.30 ꢂ 0.25 ꢂ 0.20
2.94–26.00
52072
10304
8927
0.10 ꢂ 0.10 ꢂ 0.10
2.60–26.00
31661
4628
4365
0.20 ꢂ 0.20 ꢂ 0.09
3.04–26.00
47992
7707
6293
353/0
503/6
416/0
256/0
342/2
[R(int)
]
0.0952
0.0491
0.1243
0.0660
0.1382
1.030
1.534, ꢁ1.441
0.0862
0.0494
0.1285
0.0734
0.1478
1.086
2.574, ꢁ1.476
0.0548
0.0397
0.1018
0.0479
0.1115
1.106
1.434, ꢁ1.388
0.0400
0.0236
0.0606
0.0258
0.0616
1.174
0.479, ꢁ0.922
0.0688
0.0511
0.1266
0.0657
0.1364
1.032
2.224, ꢁ1.173
a,b
R1
a,b
wR2
R1 (all data)b
wR2 (all data)b
Goodness-of-fit on F2
D
qmax,min (e Åꢁ3
)
a
I > 2
¼
r
(I).
P
P
P
P
2
1=2
bR1
kFoj ꢁ jFck= jFoj, wR2 ¼ ½ wðF2o ꢁ Fc2Þ = wFo4ꢃ
.
solution of Ph2Te2 in CDCl3 as an external standard for 125Te. The Te
NMR spectra of the reaction solutions were recorded unlocked in
EtOH. The 13C{1H} and 125Te NMR spectra of the isolated complexes
were recorded in CDCl3 that served as an internal 2H lock. Carbon
chemical shifts (ppm) are reported relative to Me4Si and tellurium
chemical shifts relative to neat Me2Te [d (Me2Te) = d
(Ph2Te2) + 422] [18].
2.4. Reaction of RhCl3 ꢀ 3H2O and Te(CH2SiMe3)2
RhCl3 ꢀ 3H2O (0.0605 g; 0.2298 mmol) was dissolved in 2 ml of
ethanol and Te(CH2SiMe3)2 (0.2430 g; 0.8045 mmol) dissolved in
2 ml of ethanol was added into the resulting solution. (metal-to-li-
gand molar ratio of 1:3½). The reaction mixture was stirred at
room temperature for 24 h. The resulting solution was cooled to
ꢁ20 °C during which time orange-red crystals of mer-
[RhCl3{Te(CH2SiMe3)2}3] (1) were formed. Yield: 0.1462 g (57%).
Anal. Calc. for C24H66Cl3RhSi6Te3 (1): C, 25.84; H, 5.96. Found: C,
2.3. X-ray crystallography
1
Diffraction data of 1–4 and 5 ꢀ ½EtOH were collected on a Non-
27.56; H, 6.33%.1 125Te NMR: 406 ppm (d, JTe-Rh = 96 Hz, Te3),
1
ius Kappa-CCD diffractometer at 120 K using graphite monochro-
369 ppm (d, JTe-Rh = 67 Hz, Te1, Te2) (intensity ratio 1:2; for the
mated Mo K
a
radiation (k = 0.71073 Å; 55 kV, 25 mA). Crystal
numbering of atoms, see Fig. 1).
data and the details of structure determinations are given in
Table 1.
When the reaction solution of RhCl3 ꢀ 3H2O (0.0605 g;
0.2298 mmol), and Te(CH2SiMe3)2 (0.2560 g; 0.8476 mmol) was
refluxed for two hours before concentration by evaporation, the
yield of the orange-red crystals of mer-[RhCl3{Te(CH2SiMe3)2}3]
(1) was 0.2024 g (79%).
The reaction and workup of the solution were repeated using a
metal-to-ligand molar ratio of 1:2½ [RhCl3 ꢀ 3H2O 0.0642 g
(0.2438 mmol) and Te(CH2SiMe3)2 0.2063 g (0.6830 mmol)]. A
mixture of orange-red crystals of mer-[RhCl3{Te(CH2SiMe3)2}3]
Structures were solved by direct methods using SIR-92 [19] and
refined using SHELXL-97 [20]. After the full-matrix least-squares
refinement of the non-hydrogen atoms with anisotropic thermal
parameters, the hydrogen atoms were placed in calculated posi-
tions in the OH group (O–H = 0.95 Å), in the aromatic rings (C–
H = 0.95 Å), in the CH3 groups (C–H = 0.98 Å) and in the CH2 groups
(C–H = 0.99 Å). The isotropic thermal parameters of the aromatic
and methylene hydrogen atoms were fixed at 1.2 times and the
methyl hydrogen atoms were fixed at 1.5 times to those of the cor-
responding carbon atom. The scattering factors for the neutral
atoms were those incorporated with the programs. One trimethyl-
silyl group in complex 2 turned out to be disordered. In the refine-
ment the disorder was taken into account by refining the site
occupation factors of the two alternative orientations and con-
straining their sums to unity. Since the site occupation factors
and thermal parameters of the disordered atoms correlate with
each other, the thermal parameters of the corresponding pairs of
atoms were restrained to be equal. A solvent molecule in the lattice
of complex 5 was also severely disordered between two symmetry
equivalent positions. This disorder was also resolved in a similar
fashion.
(1) and red crystals of [Rh2(l-Cl)2Cl4{Te(CH2SiMe3)2}4] (2) was
formed upon cooling the solution to ꢁ20 °C. Anal. Calc. for
C32H88Cl6Rh2Si8Te4 (2): C, 23.63; H, 5.45. Found: C, 23.92; H,
1
5.65%. 125Te NMR: 557 ppm (d, JTe-Rh = 102 Hz, Te1, Te2),
1
463 ppm (d, JTe-Rh = 74 Hz, Te3, Te4) (intensity ratio 1:1; for the
numbering of atoms, see Fig. 2).
The reaction solution with the metal-to-ligand molar ratio of
1:1½ [RhCl3 ꢀ 3H2O 0.0331 g (0.126 mmol) and Te(CH2SiMe3)2
0.0564 g (0.187 mmol)] was refluxed for two hours. Upon partial
evaporation of the solvent with subsequent cooling to ꢁ20 °C, dark
1
The crystals of 1 were moist containing ca. 6% of solvent ethanol, as deduced by
13C NMR. The calculated elemental analysis for this composition is C, 27.17; H, 6.42
that is consistent with the determined composition.

L. Vigo et al. / Journal of Organometallic Chemistry 694 (2009) 2053–2060
2055
Si32
Si11
Cl2
Si12
Cl1
Si21
O1
Si21
Cl5
Te1
Te3
Rh2
Cl4
Rh1
Te2
Rh1
Cl3
Te1
Te2
Cl3
Cl6
Si31
Si32
Si12
Cl1
Te3
Cl2
Si11
Si22
Si22
Si31
Fig. 1. Molecular structure of mer-[RhCl3{Te(CH2SiMe3)2}3] (1) indicating the
numbering of the atoms. The thermal ellipsoids have been drawn at 50% probability
level. Hydrogen atoms have been omitted for clarity.
Fig. 3. Molecular structure of [Rh2(l-Cl)2Cl4(OHCH2CH3){Te(CH2SiMe3)2}3] (3)
indicating the numbering of the atoms. The thermal ellipsoids have been drawn
at 50% probability level. Hydrogen atoms have been omitted for clarity.
Si12
Si41
Si4A
Te4
Cl2
Si22
Cl5
Te1
Rh1
Cl4
Rh2
Cl3
Te2
Cl2
Cl6
Si11
Te3
Cl1
S1
S3
Si21
Rh1
Si31
Si32
S2
Cl3
Fig. 2. Molecular structure of [Rh2(l-Cl)2Cl4{Te(CH2SiMe3)2}4] (2) indicating the
numbering of the atoms. The thermal ellipsoids have been drawn at 50% probability
level. Hydrogen atoms have been omitted for clarity.
Cl1
Fig. 4. Molecular structure of mer-[RhCl3(SMePh)3] (4) indicating the numbering of
the atoms. The thermal ellipsoids have been drawn at 50% probability level.
Hydrogen atoms have been omitted for clarity.
red crystals of [Rh2(l-Cl)2Cl4(OHCH2CH3){Te(CH2SiMe3)2}3] (3)
were formed. Yield: 0.0469 g (37%). Anal. Calc. for C26H72Cl6ORh2-
Si6Te3 (3): C, 22.78; H, 5.29. Found: C, 23.01; H, 5.61%. 125Te NMR:
1
1
683 ppm (d, JTe-Rh = 131 Hz, Te3), 560 ppm (d, JTe-Rh = 102 Hz,
Te1, Te2) (intensity ratio 1:2; for the numbering of atoms, see
Fig. 3).
2.6. Reaction of mer-[RhCl3(SMePh)3] and Te(CH2SiMe3)2
mer-[RhCl3(SMePh)3] (0.290 g, 0.50 mmol) was dissolved in
5 ml of ethanol and Te(CH2SiMe3)2 (0.304 g; 1.00 mmol) was added
into the resulting solution. The reaction mixture was stirred for an
hour at room temperature and then concentrated by partial evap-
oration of the solvent. The crude product was filtered off, washed
several times with cold diethyl ether, and recrystallized from
2.5. Preparation of mer-[RhCl3(SMePh)3] (4)
RhCl3 ꢀ 3H2O (0.263 g, 1.00 mmol) and an excess of SMePh
(0.752 g, 6.05 mmol) were refluxed in 10 ml of ethanol for 3.5 h.
The dark red solution was cooled at room temperature and then
to ꢁ20 °C. The resulting red crystals of mer-[RhCl3(SMePh)3] (4)
were filtered off, washed several times with cold diethyl ether,
and dried. Yield: 0.470 g (81%). Anal. Calc. for RhCl3S3C21H24 (4):
C, 43.35; H, 4.16. Found: C, 43.46; H, 3.48%. 13C{1H} NMR: 124–
128 ppm (m, phenyl groups), 19 ppm (s, C1, C2), 16 ppm (s, C3)
(for the numbering of atoms, see Fig. 4).
dichloromethane.
A mixture of orange-red crystals of mer-
[RhCl3{Te(CH2SiMe3)2}2(SMePh)] ꢀ ½CH3CH2OH (5 ꢀ ½EtOH) [125Te
1
NMR: 430 ppm (d, JTe-Rh = 75 Hz)], mer-[RhCl3{Te(CH2SiMe3)2}3]
1
1
(1) [406 ppm (d, JTe-Rh = 96 Hz), 369 ppm (d, JTe-Rh = 67 Hz)
(intensity ratio 1:2], and mer-[RhCl3(SMePh)3] (4) was obtained
upon cooling the solution to ꢁ20 °C.

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L. Vigo et al. / Journal of Organometallic Chemistry 694 (2009) 2053–2060
The molecular structure of 1 is shown in Fig. 1. The selected
3. Results and discussion
bond parameters are presented in Table 2. The lattice of 1 is built
up of discrete molecules with the coordination sphere of rhodium
a slightly distorted octahedron. The two ‘axial’ Rh–Te bonds Rh1–
Te1 and Rh1–Te2 show the lengths of 2.6129(7) and 2.6439(7) Å,
respectively. The ‘equatorial’ bond Rh1–Te3 is somewhat shorter
and shows the length of 2.5733(7) Å. The relative bond lengths
are consistent with the stronger trans-influence of tellurium com-
pared to that of chlorine and is also reflected by the smaller 1JTe-Rh
coupling constant of the more intense resonance at 369 ppm com-
pared to that of the less intense resonance at 406 ppm.
The stronger trans-influence of tellurium than that of chlorine is
also reflected by the Rh–Cl distances. Rh1–Cl1 and Rh1–Cl3 that
are in trans-position to each other show shorter lengths of
2.362(2) and 2.353(2) Å, respectively, than Rh1–Cl3 of 2.381(1) Å
that is in trans-position with respect to Te3.
3.1. The reaction of RhCl3 ꢀ 3H2O and Te(CH2SiMe3)2
The formation of the complexes and the product distribution in
the reaction of RhCl3 ꢀ 3H2O and Te(CH2SiMe3)2 are dependent on
the initial molar ratio of the reactants.
3.1.1. Metal-to-ligand molar ratio above 1:3½
When the reaction mixture employing the metal-to-ligand mo-
lar ratio above 1:3½ was carried out by stirring the reactants at
room temperature, the 125Te NMR spectrum of the reaction solu-
tion showed four resonances at 420 ppm (1JTe-Rh = 80 Hz), 406
2
2
(1JTe-Rh = 96 Hz, JTe-Te = 790 Hz), 369 ppm (1JTe-Rh = 67 Hz, JTe-Te
=
790 Hz), and 294 ppm (1JTe-Rh = 62 Hz.). Upon refluxing the reac-
tion mixture, the resonance at 420 ppm disappeared, and the rela-
tive intensity of that at 294 ppm became smaller.
The tentative assignment of the resonances at 420 ppm
(1JTe-Rh = 80 Hz) and 294 ppm (1JTe-Rh = 62 Hz) will be discussed be-
low (see Section 3.3 Tentative Assignment of Unknown Resonances).
The resonances at 406 and 369 ppm showed a relative intensity
ratio of 1:2 in spectra of both room temperature and refluxed reac-
tion mixtures. They were assigned to the mononuclear mer-
[RhCl3{Te(CH2SiMe3)2}3] (1) complex based on the X-ray structure
determination of the orange-red crystals that were obtained upon
crystallization. This assignment was verified by redissolving the
crystals in CDCl3 and re-recording the 125Te NMR spectrum.
3.1.2. Metal-to-ligand molar ratio 1:2½
Upon decreasing the relative amount of Te(CH2SiMe3)2, two
new major resonances of approximately equal intensity were ob-
served at 557 (1JTe-Rh = 102 Hz) and 463 ppm (1JTe-Rh = 74 Hz) in
Table 2
Selected bond lengths (Å) and angles (°) in mer-[RhCl3{Te(CH2SiMe3)2}3] (1), [Rh2(
l
-Cl)2Cl4{Te(CH2SiMe3)2}4] (2), and [Rh2(
l
-Cl)2Cl4(OHCH2CH3){Te(CH2SiMe3)2}3] (3).
1
2
3
Rh1–Te1
Rh1–Te2
Rh1–Te3
Rh1–Cl1
Rh1–Cl2
Rh1–Cl3
2.6129(7)
2.6439(7)
2.5733(7)
2.362(2)
2.353(2)
2.381(1)
Rh1–Te1
Rh1–Te2
Rh1–Cl1
Rh1–Cl2
Rh1–Cl5
Rh1–Cl6
Rh2–Te3
Rh2–Te4
Rh2–Cl3
Rh2–Cl4
Rh2–Cl5
Rh2–Cl6
2.5501(8)
2.5631(9)
2.348(2)
2.349(2)
2.417(2)
2.424(2)
2.6330(8)
2.6359(8)
2.325(2)
2.316(2)
2.389(2)
2.391(2)
Rh1–Te1
Rh1–Te2
Rh1–Cl1
Rh1–Cl2
Rh1–Cl5
Rh1–Cl6
Rh2–Te3
Rh2–O1
Rh2–Cl3
Rh2–Cl4
Rh2–Cl5
Rh2–Cl6
2.5539(6)
2.5539(8)
2.333(1)
2.364(1)
2.428(1)
2.454(1)
2.5192(7)
2.174(4)
2.321(1)
2.328(1)
2.380(1)
2.369(1)
Te1–Rh1–Te2
Te1–Rh1–Te3
Te1–Rh1–Cl1
Te1–Rh1–Cl2
Te1–Rh1–Cl3
Te2–Rh1–Te3
Te2–Rh1–Cl1
Te2–Rh1–Cl2
Te2–Rh1–Cl3
Te3–Rh1–Cl1
Te3–Rh1–Cl2
Te3–Rh1–Cl3
Cl1–Rh1–Cl2
Cl1–Rh1–Cl3
Cl2–Rh1–Cl3
175.03(2)
93.21(2)
89.24(4)
90.75(4)
88.60(4)
91.09(2)
88.29(4)
91.95(4)
87.20(4)
89.62(4)
87.31(4)
177.10(4)
176.93(5)
92.67(5)
90.40(5)
Te1–Rh1–Te2
Te1–Rh1–Cl1
Te1–Rh1–Cl2
Te1–Rh1–Cl5
Te1-Rh1–Cl6
Te2–Rh1–Cl1
Te2–Rh1–Cl2
Te2–Rh1–Cl5
Te2–Rh1–Cl6
Cl1–Rh1–Cl2
Cl1–Rh1–Cl5
Cl1–Rh1–Cl6
Cl2–Rh1–Cl5
Cl2–Rh1–Cl6
Cl5–Rh1–Cl6
Te3–Rh2–Te4
Te3–Rh2–Cl3
Te3–Rh2–Cl4
Te3–Rh2–Cl5
Te3–Rh2–Cl6
Te4–Rh2–Cl3
Te4–Rh2–Cl4
Te4–Rh2–Cl5
Te4–Rh2–Cl6
Cl3–Rh2–Cl4
Cl3–Rh2–Cl5
Cl3–Rh2–Cl6
Cl4–Rh2–Cl5
Cl4–Rh2–Cl6
Cl5–Rh2–Cl6
88.26(2)
86.00(5)
92.96(5)
93.45(4)
178.23(4)
91.83(5)
88.22(5)
178.11(4)
92.85(4)
178.95(6)
89.10(6)
92.58(6)
90.88(6)
88.46(6)
85.47(5)
177.92(2)
89.50(4)
90.62(5)
93.60(4)
86.21(5)
90.31(4)
87.32(5)
86.70(4)
95.86(5)
91.94(6)
175.86(6)
90.63(5)
90.77(6)
175.90(6)
86.84(5)
Te1–Rh1–Te2
Te1–Rh1–Cl1
Te1–Rh1–Cl2
Te1–Rh1–Cl5
Te1–Rh1–Cl6
Te2–Rh1–Cl1
Te2–Rh1–Cl2
Te2–Rh1–Cl5
Te2–Rh1–Cl6
Cl1–Rh1–Cl2
Cl1–Rh1–Cl5
Cl1–Rh1–Cl6
Cl2–Rh1–Cl5
Cl2–Rh1–Cl6
Cl5–Rh1–Cl6
Te3–Rh2–O1
Te3–Rh2–Cl3
Te3–Rh2–Cl4
Te3–Rh2–Cl5
Te3–Rh2–Cl6
O1–Rh2–Cl3
O1–Rh2–Cl4
O1–Rh2–Cl5
O1–Rh2–Cl6
Cl3–Rh2–Cl4
Cl3–Rh2–Cl5
Cl3–Rh2–Cl6
Cl4–Rh2–Cl5
Cl4–Rh2–Cl6
Cl5–Rh2–Cl6
94.00(2)
87.64(4)
92.33(4)
92.89(3)
175.36(3)
94.22(4)
83.27(4)
170.89(3)
89.58(3)
177.47(5)
90.02(5)
89.16(5)
90.50(5)
91.01(5)
83.86(4)
173.8(1)
83.72(4)
82.54(5)
96.70(4)
99.51(4)
90.91)
94.7(1)
88.8(1)
83.5(1)
91.36(5)
177.68(5)
90.90(5)
90.96(5)
177.10(5)
86.77(4)

L. Vigo et al. / Journal of Organometallic Chemistry 694 (2009) 2053–2060
2057
addition to those of 1. The crystallization of the reaction solution
afforded a mixture of two sets of crystals: orange-red crystals of
1 and red crystals that upon crystal structure determination was
The Rh–Te bond lengths Rh1–Te1 and Rh1–Te2 involving the
cis-tellane arrangements [2.5539(6) and 2.5539(8) Å, respectively]
agree well with those of 2. The Rh2–Te3 bond of 2.5192(7) Å is
somewhat shorter and is consistent with the weaker trans-influ-
ence of oxygen compared to that of chlorine. When comparing
the Rh–Cl bond lengths in 2 and 3, it can be concluded that the rel-
ative lengths of the corresponding bonds agree well with each
other.
shown to be dinuclear [Rh2(l-Cl)2Cl4{Te(CH2SiMe3)2}4] (2).
The molecular structure of 2 is shown in Fig. 2 and the selected
bond parameters in Table 2. The lattice of 2 is built up of discrete
dinuclear complexes in which the two rhodium centers are linked
by two bridging chloride ligands. Both rhodium centers show a
slightly distorted octahedral coordination environment. Rh1 has
two equatorial tellane ligands in cis-positions to each other and
two axial chlorido ligands in trans-positions to each other. By con-
trast, Rh2 shows two trans-tellane ligands in the axial positions
and two equatorial cis-chlorido ligands.
3.2. Ligand substitution of mer-[RhCl3(SMePh)3] by Te(CH2SiMe3)2
mer-[RhCl3(SMePh)3] (4) was prepared with good yield by
refluxing RhCl3ꢀ3H2O with an excess of SMePh in ethanol. Red crys-
tals of 4 were formed upon cooling the reaction solution. The
13C{1H} NMR spectrum of 4 that was recorded, when the crystals
of 4 were dissolved in CDCl3 displayed two sets of resonances with
the intensity ratio of 2:1, as expected for the mer-isomer contain-
ing two MePhS ligands in mutual trans-positions with each other
and one ligand in cis-position with respect to both of them. Thus,
the resonances at 19 and 16 ppm (intensity ratio 2:1) were as-
signed to the two equivalent methyl groups of the ligands in
trans-position with respect to each other and to the methyl group
of the ligand in the cis-position, respectively. The resonances of
aromatic carbon atoms were found in the range 124–128 ppm.
Their number and intensity were also consistent with the presence
of the mer-isomer.
The crystal structure determination showed that 4 is mer-
[RhCl3(SMePh)3] that is composed of discrete complexes in which
the coordination sphere around rhodium is a slightly distorted
octahedron (see Fig. 4). The selected bond lengths and angles are
shown in Table 3.
The Rh–S bond lengths span a range of 2.3561(6)–2.3623(7) Å.
They are in agreement with the Rh–S distances reported for mer-
[RhCl3(SMe2)3] [2.3283(8)–2.3660(7) Å] [23], mer-[RhCl3(SC4H8)3]
[2.333(1)–2.363(1) Å] [24], and mer-[RhCl3(SC8H8)3] [2.330(1)–
2.369(1) Å] [25]. The Rh–Cl bond lengths range 2.336(1)–
2.359(1) Å, again in agreement with those of 2.3350(7)–
2.3609(7) Å [23], 2.341(1)–2.355(1) Å [24], and 2.333(2)–2.359(1)
[25] observed in mer-[RhCl3(SMe2)3], mer-[RhCl3(SC4H8)3], and
mer-[RhCl3(SC8H8)3], respectively. The trans-influence of chlorine
and sulfur seems to be of comparable strength with possibly that
Similar structures have been reported for [Rh2(l-X)2X4(PR3)4]
(X = Cl, Br; R = Et, nBu) containing phosphine ligands [21,22]. The
isomerism of the dinuclear complexes was rationalized by Cotton
et al. [21], who concluded that the preferred isomers obeyed two
principles: (1) no l-ligand should have both of its bonds weakened
by the strong trans-influence of the phosphine ligand, and (2) for
steric reasons two phosphine ligands should not occupy adjacent
axial positions on the two rhodium atoms. However, cis-cis
arrangement has been reported for [Rh2(l-Br)2Br4(PMe3)4] with
sterically less demanding PMe3 ligands [29].
The Rh–Te bonds Rh1–Te1 and Rh1–Te2 that are in cis-positions
to each other show lengths of 2.5501(8) and 2.5631(9) Å, respec-
tively. They are shorter than the Rh2–Te3 and Rh2–Te4 bonds
[2.6330(8) and 2.6359(8) Å, respectively] that are a part of the
trans-tellane arrangement. These bond lengths again demonstrate
the relative strengths of the trans-influence of the tellurium and
chlorine atoms that is also reflected by the bridging Rh–Cl bond
lengths. The Rh1–Cl5 and Rh1–Cl6 bonds that are in trans-positions
to tellurium atoms show lengths of 2.417(2) and 2.424(2) Å,
respectively, while Rh2–Cl5 and Rh2–Cl6 that are in trans-posi-
tions to chlorine show slightly shorter lengths of 2.380(2) and
2.369(2) Å, respectively. All Rh–Cl distances are consistent with
those reported for related [Rh2(
plexes [21].
l
-Cl)2Cl4(PR3)4] (R = Et, nBu) com-
The two 125Te resonances in the NMR spectrum of the reaction
mixture can now be assigned. That at 557 ppm (1JTe-Rh = 102 Hz) is
due to the two tellurium atoms in relative cis-positions (Te1 and
Te2, see Fig. 2), and the resonance at 463 ppm (1JTe-Rh = 74 Hz) is
consequently assigned to two tellurium atoms in the relative
trans-positions (Te3 and Te4). The coupling constants are consis-
tent with the relative strengths of the trans-influence of tellurium
and chlorine.
Table 3
Selected bond lengths (Å) and angles (°) in mer-[RhCl3(SMePh)3] (4) and mer-
[RhCl3{Te(CH2SiMe3)2}2(SMePh)] ꢀ ½C2H5OH (5 ꢀ ½EtOH).
The relative intensities of the resonances in the reaction mix-
ture indicate that it contains ca. 60 mol-% of 2 and 40 mol-% of 1.
4
5
Rh1–S1
Rh1–S2
Rh1–S3
Rh1–Cl1
Rh1–Cl2
Rh1–Cl3
2.3561(6)
2.3623(7)
2.3584(6)
2.359(1)
2.336(1)
2.348(1)
Rh1–Te1
Rh1–Te2
Rh1–S1
Rh1–Cl1
Rh1–Cl2
Rh1–Cl3
2.6479(8)
2.6383(9)
2.336(2)
2.356(2)
2.333(2)
2.345(2)
3.1.3. Metal-to-ligand molar ratio of 1:1½
When the relative amount of the ligand was reduced even fur-
ther (metal-to-ligand molar ratio of 1:1½), the 125Te NMR spec-
trum of the reaction mixture exhibited two doublets at 683 ppm
(1JTe-Rh = 131 Hz) and 560 ppm (1JTe-Rh = 102 Hz) with the relative
intensity ratio of 1:2.
The crystallization of the reaction solution afforded dark red
crystals of [Rh2(l-Cl)2Cl4(OHCH2CH3){Te(CH2SiMe3)2}3] (3). The
S1–Rh1–S2
S1–Rh1–S3
S1–Rh1–Cl1
S1–Rh1–Cl2
S1–Rh1–Cl3
S2–Rh1–S3
S2–Rh1–Cl1
S2–Rh1–Cl2
S2–Rh1–Cl3
S3–Rh1–Cl1
S3–Rh1–Cl2
S3–Rh1–Cl3
Cl1–Rh1–Cl2
Cl1–Rh1–Cl3
Cl2–Rh1–Cl3
172.99(2)
92.12(2)
88.71(3)
92.86(3)
92.76(2)
94.21(2)
94.20(3)
84.46(3)
80.78(2)
90.69(2)
87.23(2)
174.39(2)
177.44(2)
92.18(2)
89.76(2)
Te1–Rh1–Te2
Te1–Rh1–S1
Te1–Rh1–Cl1
Te1–Rh1–Cl2
Te1–Rh1–Cl3
Te2–Rh1–S1
Te2–Rh1–Cl1
Te2–Rh1–Cl2
Te2–Rh1–Cl3
S1–Rh1–Cl1
S1–Rh1–Cl2
S1–Rh1–Cl3
Cl1–Rh1–Cl2
Cl1–Rh1–Cl3
Cl2–Rh1–Cl3
173.15(2)
98.37(5)
88.84(4)
85.59(5)
90.35(5)
88.20(5)
92.92(4)
90.35(5)
87.79(5)
91.80(6)
84.68(7)
175.73(6)
176.24(7)
89.84(5)
93.76(6)
molecular structure of 3 is shown in Fig. 3 and the selected bond
parameters in Table 2.
The lattice of 3 is also built up with discrete dinuclear com-
plexes in which the two octahedral rhodium centers are linked
with bridging chlorido ligands. Rh1 shows two cis-tellane ligands
in the equatorial plane in a similar fashion to 2. Rh2 has one axial
tellane ligand with a solvent ethanol molecule coordinated to the
metal in the trans-position. Like in the case of 2, the chlorido li-
gands Cl3, Cl4, Cl5, and Cl6 lie in the equatorial plane, while Cl1
and Cl2 occupy axial positions (see Figs. 2 and 3).

2058
L. Vigo et al. / Journal of Organometallic Chemistry 694 (2009) 2053–2060
Table 4
The observed and calculated 125Te chemical shifts of mononuclear [RhClx{ERR0)6ꢁx
]
(E = S, Te; R, R0 = alkyl groups) complexes.
c
Complex
vta
R
vcb
dobs (ppm)
dcalc (ppm)
Si12
[RhCl3{Te(CH2SiMe3)2}2(SMePh)]d
fac-[RhCl3(TeC4H8)3]e
2.10
3.16
3.16
3.16
3.16
2.10
2.10
2.10
12.06
10.52
10.52
10.52
10.52
11.58
11.58
10.52
430
429
420
416f
406
369
359f
294
422
413
413
413
413
381
381
290
Si11
fac-[RhCl3{Te(CH2SiMe3)2}3]e
mer-[RhCl3(TeC4H8)3]e
mer-[RhCl3{Te(CH2SiMe3)2}3]e
mer-[RhCl3{Te(CH2SiMe3)2}3]d
mer-[RhCl3(TeC4H8)3]d
Te1
trans-[RhCl2{Te(CH2SiMe3)2}4]d
a
Pauling electronegativities [26] of the donor atoms in trans-position to the
observed 125Te nuclei.
b
Cl1
The sum of Pauling electronegativities [26] of the four cis-donor atoms.
See Eq. (1).
Cl2
c
d
trans-Te–Rh–Te arrangement.
e
trans-Te–Rh–Cl arrangement (the observable 125Te nuclei are indicated in bold).
f
Rh1
Te2
Ref. [8].
S1
Cl3
of sulfur slightly stronger. Therefore, there are no clear trends in
the relative lengths of the Rh–S and Rh–Cl bonds with respect to
the identity of the ligand that lies trans to it.
The treatment of mer-[RhCl3(SMePh)3] (4) with two equivalents
of Te(CH2SiMe3)2 affords a mixture of mer-[RhCl3{Te(CH2SiMe3)2}3]
(1) and mer-[RhCl3{Te(CH2SiMe3)2}2(SMePh)] (5). Some unreacted
4 is also found in the reaction solution. The complex 5 exhibits a
Si21
1
125Te resonance at 430 ppm (1JTe-Rh = 75 Hz). The JTe-Rh coupling
Si22
constant is consistent with that of mutually trans-tellane ligands
in 1. The reaction of mer-[RhCl3(SMePh)3] (4) and Te(CH2SiMe3)2
is similar to the ligand substitution of SRPh (R = Ph, Me) in
[MCl2(SRPh)2] (M = Pt, Pd) by Te(CH2SiMe3)2 that affords a mixture
of complexes containing [MCl2(SRPh)2], [MCl2(SRPh){Te(CH2-
SiMe3)2}], and [MCl2{Te(CH2SiMe3)2}2] [17].
Fig. 5. Molecular structure of mer-[RhCl3{Te(CH2SiMe3)2}2(SMePh)] ꢀ ½CH3CH2OH
(5 ꢀ ½EtOH) indicating the numbering of the atoms. The thermal ellipsoids have
been drawn at 50% probability level. Hydrogen atoms and the disordered solvent
molecule have been omitted for clarity.
The recrystallization of the crude product from dichlorometh-
ane enabled the visual separation of orange-red crystals from the
dinuclear complexes
mononuclear complexes
Cl
Cl
Te
Cl
Te
Rh
Te
Cmpd 2 and 3
Cl Cl
Cmpd 5
Te
Cmpd 1
Cl
Cl
Cl
Cl
Te
Cl
Cl
Te
Rh
Te
Rh
Te
Cl
Rh
Cl
S
Te Te
Cmpd 3
O
Cmpd 2
Te
Cmpd 1
Te
+
Te
Rh
Te
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Te
Te
Cl
Cl
Te
Rh
Te
Rh
Te
Rh
Te
ppm
0
700
60
300
0
50
400
Fig. 6. The assignment of resonances in the 125Te chemical shifts of mononuclear and dinuclear bis(trimethylsilylmethyl)tellanerhodium complexes. Solid lines together with
black structural formulae indicate definitely assigned chemical shifts and the fragmented lines with gray structural formulae indicate tentatively assigned chemical shifts.

L. Vigo et al. / Journal of Organometallic Chemistry 694 (2009) 2053–2060
2059
solid mixture that upon crystal structure determination turned out
to be
mer-[RhCl3{Te(CH2SiMe3)2}2(SMePh)] ꢀ ½CH3CH2OH
be seen that the 125Te chemical shifts of mononuclear complexes
occur at low frequencies (below 450 ppm), whereas those of the
dinuclear complexes are found at higher frequencies (above
450 ppm).
(5 ꢀ ½EtOH) with the two tellane ligands in trans-positions with re-
spect to each other. The molecular structure of 5 is shown in Fig. 5
and the selected bond lengths in Table 3. The Rh–S bond is trans to
the chlorine atom and shows the length of 2.336(2) Å, which is
consistent with other Rh–S bonds considered in this work. The
Rh1–Te1 and Rh1–Te2 bonds of 2.6479(8) Å and 2.6383(9) Å are
of the comparable length to the Rh2–Te3 and Rh2–Te4 in 2 that
are also in mutual trans-positions to each other.
The resonance at 420 ppm (1JTe-Rh = 80 Hz) can be assigned to
fac-[RhCl3{Te(CH2SiMe3)2}3]. It is seen from Fig. 6 that this reso-
nance is found in the region of mononuclear complexes. The pres-
ence of both the mer- and fac-isomers in solution has been
reported for [RhCl3(TeC4H8)3] [8] (mer-isomer: d = 416 ppm,
1JTe-Rh = 95 Hz; d = 359 ppm, 1JTe-Rh = 72 Hz; fac-isomer d =
1
429 ppm, JTe-Rh = 92 Hz) and [RhCl3(TeC8H8)3] [7] (mer-isomer:
1
1
3.3. Tentative assignment of unknown resonances
d = 620 ppm, JTe-Rh = 70 Hz; d = 581 ppm, JTe-Rh = 70 Hz; fac-iso-
mer d = 592 ppm, JTe-Rh = 90 Hz.). The 125Te NMR spectroscopic
1
The definite assignment of 125Te resonances to complexes 1–3
and 5 enables discussion of the tentative assignment of the two
125Te resonances at 420 and 294 ppm that were observed in the
reaction of RhCl3 ꢀ 3H2O and Te(CH2SiMe3)2 (metal-to-ligand ratio
of 1:3½).
data for the two mer-isomers are in agreement with those for 1.
Those for the two fac-isomers are also consistent with the assign-
ment of the resonance at 420 ppm to fac-[RhCl3{Te(CH2SiMe3)2}3].
It can also be deduced from Fig. 6 that the resonance at
294 ppm is due to a tellane ligand in a mononuclear complex.
The appearance of only one resonance indicates that if there are
more than one tellane ligand coordinated to rhodium, they all must
The 125Te chemical shifts of the complexes 1–3 and 5 have been
summarized in Fig. 6 together with the unknown resonances. It can
1
be equivalent, The small JTe-Rh coupling constant of 62 Hz implies
that there must be pairs of tellane ligands that are in trans-posi-
tions with respect to each other. Furthermore, there was an excess
of ligand in the reaction solution that gave rise to the species dis-
playing this resonance. Therefore, this complex could be expected
to be tellane-rich.
mer + mer
L
Cl
Cl
Rh
Cl
OH2
Rh
Cl
Cl
Cl
Cl
L
L
H2O
Cl
OH2
OH2
Cl
Cl
Cl
Rh
Rh
-6 H2O
+ 4 L
+
+
+
+
+
OH2
In complexes containing similar tellane ligands, i.e. 1, 5, fac-
[RhCl3{Te(CH2SiMe3)2}3], mer- and fac-isomers [RhCl3(TeC4H8)3]
[8], the 125Te chemical shifts are dependent on the Pauling electro-
negativities of the donor atoms. Because of the significance of the
trans-influence, the electronegativity of the donor atom in the
trans-position to the observed 125Te nucleus is considered sepa-
rately from the sum of the electronegativities of the four donor
atoms in cis-positions. The least-squares fit of the definitely as-
signed chemical shifts results in the following relationship:
X
A
B
C
OH2
OH2
L
L
Cl
L
OH2
Cl
Cl
Cl
Cl
Cl
Cl
-6 H2O
+ 4 L
Cl
Cl
Cl
H2O
Cl
Cl
Rh
Rh
Rh
Rh
OH2
Cl
L
L
L
L
OH2
OH2
OH2
OH2
-6 H2O
+ 4 L
L
Cl
Cl
Cl
L
H2O
Cl
Cl
H2O
Cl
Cl
Rh
Rh
Rh
Rh
Cl
OH2
OH2
Cl
Cl
Cl
L
Cl
Cl
Cl
OH2
-6 H2O
+ 4 L
L
L
Cl
L
H2
O
OH2
Cl
Rh
Rh
dð125TeÞ ¼ 116 ꢀ vt þ 85 ꢀ
vc ꢁ 851
ð1Þ
Rh
Cl
OH2
Cl
D
E
Cl
Cl
H2O
Rh
H2
O
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
where vt is the Pauling electronegativity [26] of the donor atom in
trans-position to the observed 125Te nucleus, and
R
vc is the sum of
-6 H2O
+ 4 L
H2O
H2O
Cl
H2O
Cl
OH2
OH2
L
L
Cl
Cl
L
L
Rh
Cl
Rh
Cl
Rh
Cl
Rh
Cl
Pauling electronegativities of the four cis-donor atoms. The compar-
ison of the observed and calculated 125Te chemical shifts are shown
in Table 4.
OH2
This semi-quantitative correlation shows that the shielding of
tellurium expectedly decreases with the increasing electronega-
tivity of the donor atoms and can be used to discuss the assign-
ment of the resonance at 294 ppm. The low frequency chemical
shift at 294 ppm therefore indicates that both the electronegativ-
ity of the donor atom in trans-position and that of the four cis-
donor atoms must be rather low. One possibility for the species
giving rise to the observed 125Te chemical shift is trans-
[RhCl2{Te(CH2SiMe3)2}4]+ with a Clꢁ counter ion (see Table 4).
Analogous chalcogenoether complexes are known, as exemplified
by [RhCl2{o-C6H4(CH2EMe2)2}2]Y (E = S or Se, Y = PFꢁ6 ; E = Te,
Y = Clꢁ) [27].
mer + fac
OH2
OH2
L
L
-6 H2O
+ 4 L
H2O
Cl
OH2
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
L
Rh
Rh
F
Rh
Rh
OH2
+
+
Cl
Cl
OH2
OH2
L
L
Cl
L
OH2
-6 H2O
+ 4 L
L
Cl
Cl
L
H2O
Cl
Cl
H2O
Cl
OH2
Cl
G
Rh
Cl
Rh
Cl
Rh
Cl
Rh
Cl
Cl
Cl
OH2
fac + fac
3.4. Formation and isomerism of dinuclear complexes
Cl
L
OH2
Rh
Cl
-6 H2O
+ 4 L
Cl
Cl
Cl
L
H2O
Cl
OH2
Cl
Cl
Rh
Cl
Rh
Rh
Whereas there is no report of the crystal structure of RhCl3 ꢀ
3H2O, it can be thought to exist as two isomers: mer-[RhCl3(OH2)3]
and fac-[RhCl3(OH2)3]. Its reaction with Te(CH2SiMe3)2 can be
thought to proceed, as follows.
With an excess of Te(CH2SiMe3)2 in the reaction (the metal-to-
ligand molar ratio of 1:3½), the resonances of mer-[RhCl3{Te(CH2-
SiMe3)2}3] (1) and fac-[RhCl3{Te(CH2SiMe3)2}3] are observed in the
125Te NMR spectrum. This indicates a straight-forward ligand
H
I
L
Cl
H2O
OH2
+
+
Cl
Cl
L
Cl
Cl
OH2
Cl
Cl
-6 H2O
+ 4 L
Cl
Rh
Cl
Cl
Cl
Cl
L
H2O
Cl
OH2
Cl
Rh
L
Rh
L
Rh
H2O
OH2
L
Cl
OH2
OH2
Fig. 7. The formation of the nine possible isomers of [Rh2Cl6L4] (A–I) from mer- and
fac-isomers of [RhCl3(OH2)3].

2060
L. Vigo et al. / Journal of Organometallic Chemistry 694 (2009) 2053–2060
substitution reaction of three H2O ligands in mer-[RhCl3(OH2)3] or
fac-[RhCl3(OH2)3] by three Te(CH2SiMe3)2 molecules.
Acknowledgment
The formation of the dinuclear complexes can be thought to
proceed in two steps. The first step involves the formal condensa-
tion of the mononuclear [RhCl3(OH2)3] complexes into dinuclear
chlorido-bridged complexes [28], and the second step involves
the ligand substitution of aqua ligands either by tellane or ethanol
Financial support from Academy of Finland and the Ministry of
Education (L.V.) is gratefully acknowledged.
Appendix A. Supplementary material
CCDC 713502, 713503, 713504, 713505 and 713506 contain the
supplementary crystallographic 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. Supplemen-
tary data associated with this article can be found, in the online
version, at doi:10.1016/j.jorganchem.2009.02.001.
2½RhCl3ðOH2Þ3ꢃ ꢀ ½Rh2ð
½Rh2ð -ClÞ2Cl4ðOH2Þ4ꢃ þ 4L ꢀ ½Rh2ð
By using the argumentation of Cotton et al. [21], there are
nine possible isomers of [Rh2( -Cl)2Cl4(OH2)4] assuming that
the oxidation state of both rhodium centers is +III. Their forma-
tion from mer- and fac-isomers of [RhCl3(OH2)3] is shown in
Fig. 7. As discussed above, the reaction of [RhCl3(OH2)3] with
an excess of Te(CH2SiMe3)2 affords mostly mer-[RhCl3{Te(CH2-
SiMe3)2}3] (1) with only some fac-isomer. It can therefore be
concluded that mer-[RhCl3(OH2)3] is likely to be the major reac-
tant in the reaction solution. Thus, only the five condensation
reactions involving two mer-[RhCl3(OH2)3] complexes are rele-
vant for the production of dinuclear complexes. The observation
l
-ClÞ2Cl4ðOH2Þ4ꢃ þ 2H2O
l
l
-ClÞ2Cl4L4ꢃ þ 4H2O
l
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of only the isomer A in both [Rh2(l-Cl)2Cl4{Te(CH2SiMe3)2}4] (2)
and [Rh2( -Cl)2Cl4 (OHCH2CH3){Te(CH2SiMe3)2}3] (3) indicates
l
that only the first condensation reaction in Fig. 7 takes place.
The formation of isomer A is consistent with the reasoning of
Cotton et al. [21].
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214.
4. Conclusions
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(1993) 343.
RhCl3 ꢀ 3H2O was treated with Te(CH2SiMe3)2 in different molar
ratios. By using an excess of the tellane (metal-to-ligand molar ra-
tio of 1:3½), a mononuclear mer-[RhCl3{Te(CH2SiMe3)2}3] (1) was
observed as the main product. By reducing the metal-to-ligand
molar ratio, dinuclear [Rh2(
tained in addition to 1. Further reduction of the metal-to-ligand ra-
tio resulted in the formation of [Rh2( -Cl)2Cl4(OHCH2CH3)
l-Cl)2Cl4{Te(CH2SiMe3)2}4] (2) was ob-
l
[20] G.M. Sheldrick, Acta Crystallogr. 64A (2008) 112.
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{Te(CH2SiMe3)2}3] (3). The complexes were characterized by
X-ray crystallography and 125Te NMR spectroscopy.
The addition of Te(CH2SiMe3)2 to the solution of mer-
[RhCl3(SMePh)3] (4) yielded a mixture of 4, mer-[RhCl3{Te(CH2-
SiMe3)2}3] (1), and mer-[RhCl3(SMePh){Te(CH2SiMe3)2}2] (5Å). The
complexes 4 and 5 ꢀ ½EtOH were also characterized by X-ray crys-
tallography and NMR spectroscopy.
The trends in the 125Te chemical shifts and 1JTe-Rh coupling con-
stants enabled the tentative identification of fac-[RhCl3{Te(CH2-
SiMe3)2}3] and trans-[RhCl2{Te(CH2SiMe3)2}4]Cl among the
reaction products.
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