Trialkylphosphine-stabilized copper - Phenyltellurolate complexes: From small molecules to nanoclusters via condensation reactions

Article abstract of DOI:10.1021/ic001260k

Reactions of CuCl with Te(Ph)SiMe₃ and solublizing trialkylphosphine ligands afford a series of polynuclear copper-phenyltellurolate complexes that has been structurally characterized. The formation of the complexes is found to be highly dependent on the ancillary phosphine ligand used. The synthesis and structures of [Cu₂(μ-TePh)₂(PMe₃)₄] 1, [Cu₄(μ₃-TePh)₄(PPrⁱ ₃)₃] 2, [Cu₅(μ-TePh)₃(μ₃-TePh) ₃(PEt₃)₃][PEt₃Ph] 3, and [Cu₁₂Te₃(μ₃-TePh)₆-(PEt ₃)₆] 4 are described. The telluride (Te^2-) ligands in 4 arise from the generation of TePh₂ in the reaction mixtures. The subsequent co-condensation of clusters 3 and 4 leads to the generation of the nanometer sized complex [Cu₂₉Te₉(μ₃-TePh)₁₀(μ ₄-TePh)₂(PEt₃)₈][PEt ₃Ph] 5 in good yield, in addition to small amounts of [Cu₃₉-(μ₃-TePh)₁₀(μ₄- TePh)Te₁₆(PEt₃)₁₃] 6. These complexes are formed via the photo elimination of TePh₂. The cyclic voltammogram of 5 in THF solution exhibits two oxidation waves, assigned to the oxidation of the Cu(I) centers.

Full text of DOI:10.1021/ic001260k

4678
Inorg. Chem. 2001, 40, 4678-4685
Trialkylphosphine-Stabilized Copper-Phenyltellurolate Complexes: From Small Molecules
to Nanoclusters via Condensation Reactions
Marty W. DeGroot, Michael W. Cockburn, Mark S. Workentin, and John F. Corrigan*
Department of Chemistry, The University of Western Ontario, London, Ontario, N6A 5B7 Canada
ReceiVed NoVember 14, 2000
Reactions of CuCl with Te(Ph)SiMe3 and solublizing trialkylphosphine ligands afford a series of polynuclear
copper-phenyltellurolate complexes that has been structurally characterized. The formation of the complexes is
found to be highly dependent on the ancillary phosphine ligand used. The synthesis and structures of [Cu2(µ-
TePh)2(PMe3)4] 1, [Cu4(µ3-TePh)4(PPri3)3] 2, [Cu5(µ-TePh)3(µ3-TePh)3(PEt3)3][PEt3Ph] 3, and [Cu12Te3(µ3-TePh)6-
(PEt3)6] 4 are described. The telluride (Te2-) ligands in 4 arise from the generation of TePh2 in the reaction
mixtures. The subsequent co-condensation of clusters 3 and 4 leads to the generation of the nanometer sized
complex [Cu29Te9(µ3-TePh)10(µ4-TePh)2(PEt3)8][PEt3Ph] 5 in good yield, in addition to small amounts of [Cu39-
(µ3-TePh)10(µ4-TePh)Te16(PEt3)13] 6. These complexes are formed via the photo elimination of TePh2. The cyclic
voltammogram of 5 in THF solution exhibits two oxidation waves, assigned to the oxidation of the Cu(I) centers.
Introduction
It has been demonstrated that metal-chalcogenolate M(ER)x
complexes can be used as single source precursors to binary
solid-state materials via the elimination of ER2.4 Arnold and
co-workers also demonstrated that the Lewis base-induced
elimination of TeR2 from homoleptic metal-tellurolates leads
to the formation of metal-telluride complexes.5 We demon-
strated that photochemical-induced condensation reactions of
phosphine-stabilized copper-tellurolate cluster can lead to the
generation of higher nuclearity complexes6 and recent work by
Fenske and co-workers illustrated the general applicability of
using arylselenolate ligands to effectively stabilize copper-
The chemistry of metal-selenolate and metal-tellurolate
polynuclear (cluster) complexes continues to attract considerable
attention. The demonstrated ability of the heavier chalcogenolate
ligands, either alone or in conjunction with other (eg. phosphine)
ligands, to stabilize a variety of skeletal geometries is making
them an increasingly important method for binary nanocluster
synthesis.1 Despite the surge in the development of this area of
chemistry, the synthesis and structural characterization of
nanoscale metal-tellurium cluster complexes2 remains under-
developed relative to their selenium congeners. This may be
attributed, in part, to the instability and difficulty of handling
Te(SiMe3)2 compared to Se(SiMe3)2, the latter reagent finding
widespread use as an excellent source of Se2- in the synthesis
of metal-selenide nanoclusters and colloids.3 Steigerwald and
co-workers have demonstrated the utility of trialkylphosphine
tellurides (R3PdTe) as a source of soluble “Te(0)” to form
numerous high-nuclearity, metal-telluride polynuclear com-
plexes, when treated with suitable metal(0) reagents.2c-f
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S.; Fenske, D. Ber. Bunsen Phys. Chem. 1997, 101, 1588-1592. (f)
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Allg. Chem. 2000, 626, 338-348. (b) Fenske, D.; Steck, J.-C. Angew.
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30, 2256-2257. (f) Brennan, J. G.; Siegrist, T.; Carroll, P. J.;
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10.1021/ic001260k CCC: $20.00 © 2001 American Chemical Society
Published on Web 07/27/2001

Copper-Phenyltellurolate Complexes
Inorganic Chemistry, Vol. 40, No. 18, 2001 4679
selenide and silver-selenide “giant” clusters.7 The ability of
E(R)- and E(Ar)- ligands to bridge two, three, and even four
metal centers has resulted in a wide variety of structural types
being isolated and structurally characterized.
We wished to further probe facile condensation routes into
high-nuclearity metal-telluride complexes starting with “low
nuclearity” precursors. Herein we describe the synthesis and
characterization of several phosphine-stabilized copper-phenyl-
tellurolate complexes including two high-nuclearity copper-
telluride clusters [Cu29(TePh)12Te9(PEt3)8][PEt3Ph] 5 and
[Cu39(TePh)11Te16(PEt3)] 6, formed from the co-condensation
of the complexes [Cu12Te3(TePh)6(PEt3)6] 3 and [Cu5(TePh)6-
(PEt3)3][PEt3Ph] 4.
λonset ) 460 nm. Selected IR data (KBr): 3048w, 2952m, 1569m,
1467m, 1429m, 1291m, 1261w, 1092m, 1058s, 881m, 802s.
Synthesis of [Cu5(TePh)6(PEt3)3][PEt3Ph] 3 and [Cu12Te3(TePh)6-
(PEt3)6] 4. PEt3 (0.49 mL, 3.3 mmol) was added to a suspension CuCl
(0.33 g, 3.3 mmol) in pentane (20 mL) and stirred for 45 min. Te-
(Ph)SiMe3 (0.93 mL, 4.0 mmol) was then added to yield a bright yellow,
homogeneous solution. After stirring for 1 h, the yellow solution was
allowed to stand undisturbed. The solution gradually darkened to a dark
green in color and small, yellow-orange, needlelike crystals of 3 formed
overnight. After a few more days, dark green, hexagonal prisms of 2
appeared. It was observed that the formation of these metal clusters
seemed to proceed more quickly in the presence of direct sunlight.
The crystals were isolated (0.22 g), washed with pentane and separated
manually. Yield: 3 0.09 g (8%, based on Cu) and 4 0.13 g (15%, based
on Cu). Anal. Calcd for C66H95P4Cu5Te6: C, 37.8; H, 4.57. Found: C,
37.6; H, 5.15. Anal. Calcd for C72H120P6Cu12Te9: C, 28.1; H, 3.92.
Found: C, 28.5; H, 4.01. Data for 3 NMR (δ, C6D6): 1H 8.19 (br s, 12
Experimental Section
Standard Schlenk line and drybox techniques8 were employed
throughout with high-purity, dried nitrogen. Solvents for reactions and
crystallizations were distilled under nitrogen from appropriate drying
agents prior to use. Diethyl ether, tetrahydrofuran, hexane and pentane
were dried over sodium/benzophenone. Trialkylphosphines9a-c and Te-
Hphenyl), 7.92, d, JHH ) 7 Hz, 2 Hphenyl), 7.06-6.78 (mult, 21 Hphenyl),
2.11 (dq, JHH ) 7 Hz, JPH ) 12 Hz, 6 HCH2), 1.45 (br s, 18 HCH2), 0.95
(br s, 27 HCH3), 0.37 (dt, JHH ) 7 Hz, JPH ) 19 Hz, 9 HCH3) ppm;
31P{1H} 35.5(s), -19.4 (br s, W1/2 ) 58 Hz) ppm. Mp: 131 °C
(decomp). UV-vis (THF): broad featureless spectrum, with increasing
absorbance from λonset ) 470 nm. Selected IR data (CHCl3): 2963m,
1559m, 1472m, 1261s, 1205m, 1099s, 1016s, 800s. Data for 4 NMR
(δ, C6D6): 1H 8.17 (d, JHH ) 8 Hz, 12 Hphenyl), 7.06 (vt, JHH ) 7 Hz,
6Hphenyl), 6.99 (vt, JHH ) 7 Hz, 12Hphenyl), 1.33 (mult, 36HCH2), 0.92
(dt, JHH ) 8 Hz, JPH ) 14 Hz, 54HCH3) ppm; 31P{1H} -14.8 (br s,
W1/2 ) 27 Hz) ppm. Mp: 145-146 °C. UV-vis (THF): λmax ) 640,
440 nm. Selected IR data (KBr): 3046w, 2962m, 2925w, 1569m,
1469m, 1261s, 1097s, 1033s, 1015s, 802s.
(Ph)SiMe3 were prepared by literature procedures. H and 31P{1H}-
NMR spectra were obtained on a Varian Mercury 400 (operating
frequencies 400.09 and 161.96 MHz, respectively) or Inova 400
(operating frequencies 399.76 and 161.83 MHz, respectively) spec-
9d
1
1
trometer. H spectra were referenced to residual protio impurities of
the deuterated solvents, while 31P{1H} spectra were referenced exter-
nally to H3PO4. UV-vis spectra were recorded on a Varian Cary 100
spectrometer, scanning from 700 to 200 nm. Infrared spectra were
recorded on a Nicolet Avatar 3200 FTIR spectrometer. Reported melting
points are uncorrected. Chemical analyses were performed by Chemisar
Laboratories (Guelph, Ontario) and the Institut fu¨r Anorganische
Chemie, Karlsruhe, Germany.
Synthesis of [Cu2(TePh)2(PMe3)4] 1. A total of 0.15 g (1.5 mmol)
of CuCl and 0.31 mL (3.0 mmol) of PMe3 were mixed in 5 mL of
THF to form a clear solution. To the solution was added 0.35 mL (1.5
mmol) of Te(Ph)SiMe3 to yield a yellow/pale green solution. The
solution was stirred for 40 min and layered with hexane. Yellow crystals
of 1 grew at room temperature within 2-3 days. Yield: 0.33 g (55%).
Anal. Calcd for C24H46P4Cu2Te2: C, 34.3; H, 5.51. Found: C, 34.6;
H, 5.61. NMR (δ, C6D6): 1H 8.32 (d, JHH ) 7 Hz, 4Hphenyl), 7.00 (vt,
JHH ) 7 Hz, 2Hphenyl), 6.87 (vt, JHH ) 7 Hz, 4Hphenyl), 0.91 (d, JPH ) 4
Hz, 36 HCH3) ppm; 31P{1H} -44.5 (s, W1/2 ) 204 Hz) ppm. Mp: 86°
C (decomp). UV-vis (THF): broad featureless spectrum, with increas-
ing absorbance from λonset ) 470 nm. Selected IR data (KBr): 3045w,
2961m, 2925w, 1569m, 1469m, 1261s, 1096s, 1032s, 1015s, 802s.
Synthesis of [Cu29Te9(TePh)12(PEt3)8][PEt3Ph] 5 and [Cu39-
(TePh)11Te16(PEt3)13] 6. Cluster [Cu29(TePh)12Te9(PEt3)8][PEt3Ph] 5
was prepared from the co-condensation reaction of the two smaller
clusters 3 and 4. Cluster 3 (0.09 g, 0.043 mmol) and cluster 4 (0.19 g,
0.062 mmol) were dissolved in 6.5 mL THF to yield a dark green-
yellow solution. The solution was stirred for 24 h and the resulting
deep wine-red solution was then layered with diethyl ether via slow
diffusion. After a few days, purple crystals of 5 formed. The solvent
was removed and the crystals washed with two small portions of diethyl
ether (10 mL). Yield: 42% (0.12 g). Crystals of 6 formed in the mother
liquor after an additional 48-72 h (Yield: ∼ 2%). When this
experiment was attempted in the absence of light, there was no evidence
for the formation of 5 (or 6). NMR analysis of the mother liquor
confirmed the presence of TePh2 in the reaction mixture. Anal. Calcd
for C132H200P9Cu29Te21: C, 24.1; H, 3.06. Found: C, 24.1; H, 3.22.
Anal. Calcd for C144 H250P13Cu39Te27: C, 20.8; H, 3.03. Found: C,
19.0; H, 2.67; 31P{1H} NMR data for 5 (δ, C6D6/C4H8O): 38.1 (s),
-15.6 (br s, W1/2 ) 145 Hz), -18.3 (br s, W1/2 ) 175 Hz) ppm. Mp:
5, 171 °C (decomp); 6, >300 °C. UV-vis data for 5 and 6 are discussed
in the text. Selected IR data for 5 (KBr): 3046w, 2962m, 2923w,
1569m, 1469m, 1261s, 1097s, 1033s, 1015s, 802s. Selected IR data
for 6 (KBr): 3043w, 2958m, 2927w, 1569m, 1469m, 1033m, 1015m,
766m, 727m.
Synthesis of [Cu4(TePh)4(PPri3)3] 2. A total of 0.32 g (3.2 mmol)
of CuCl was dissolved in 15 mL of Et2O with 1.23 mL (6.5 mmol) of
PPri3. To the solution was added 0.75 mL (3.2 mmol) of Te(Ph)SiMe3
to yield a bright yellow homogeneous solution. The solution was stirred
1
for 5 min. The solvent was reduced by ∼ /2 in volume and bright yellow
crystals of 2 grew within a few hours. Yield: 0.45 g (35%). Anal. Calcd
for C51H83P3Cu4Te4: C, 39.4; H, 5.38. Found: C, 39.4; H, 5.32. NMR
(δ, C6D6): 1H 8.11 (d, JHH ) 7 Hz, 8Hphenyl), 6.99 (vt, JHH ) 7 Hz,
4Hphenyl), 6.85 (vt, JHH ) 7 Hz, 8Hphenyl), 1.89 (br s, 9HCH), 1.09 (mult,
54HCH3) ppm; 31P{1H} 20.6 (s, W1/2 ) 45 Hz) ppm. Mp: 155 °C. UV-
vis (THF): broad featureless spectrum, with increasing absorbance from
Electrochemical Experiments. Cyclic voltammetry was performed
using a PAR 263 potentiostat interfaced to a personal computer using
PAR 270 electrochemistry software. The electrochemical cell was
contained in an inert atmosphere glovebox at room temperature to
prevent air and moisture contamination to the sample. In a typical
experiment 1 or 2 mM of solute was added to dry THF solvent
containing 0.1-0.2 M tetrabutylammonium tetrafluoroborate as the
electrolyte. Prior to each experiment the working electrode, a 0.5 mm
diameter platinum (Pt) electrode, was freshly polished with 1 µ diamond
paste and ultrasonically cleaned in ethanol for fifteen minutes. The
counter electrode was a platinum flag and the reference a silver wire
immersed in a glass tube containing electrolyte in THF with a fine
sintered ceramic bottom. Ferrocene was used as an internal redox
reference, and thus the potentials can be referenced to the Ag/AgCl/
KCl reference electrode: Fc/Fc+ ) 0.629V.10 To compensate for the
cells internal resistance, the iR compensation was adjusted to at least
96% of the oscillation value.
(7) (a) Bettenhausen, M.; Eicho¨fer, A.; Fenske, D.; Semmelmann, M. Z.
Anorg. Allg. Chem. 1999, 625, 593-601. (b) Zhu, N.; Fenske, D. J.
Chem. Soc., Dalton Trans. 1999, 1067-1075. (c) Fenske, D.; Zhu,
N.; Langetepe; T. Angew. Chem., Intl. Ed. Engl. 1998, 37, 2640-
2644.
(8) Errington, R. J. AdVanced Practical Inorganic and Metalorganic
Chemistry; Blackie Academic and Professional: London, 1997.
(9) (a) Sasse, K. In Methoden der Organischen Chemie, Band 1; Houben-
Weyl, Ed.; Thieme Verlag: Stuttgart, 1963; p 32. (b) Kaesz, H. D.;
Stone, F. G. A. J. Org. Chem. 1959, 24, 635-637. (c) Cumper, C.
W. N.; Foxton, A. A.; Read, J.; Vogel, A. I. J. Chem. Soc. 1964,
430-434. (d) Drake, J. E.; Hemmings, R. T. Inorg. Chem. 1980, 19,
1879-1883.

4680 Inorganic Chemistry, Vol. 40, No. 18, 2001
DeGroot et al.
Table 1. Crystallographic Data for the Structure Determinations of [Cu2(TePh)2(PMe3)4] 1, [Cu4(TePh)4(PPri3)3] 2, [Cu5(TePh)6(PEt3)3][PEt3Ph]
3, [Cu12Te3(TePh)6(PEt3)6] 4, [Cu29Te9(TePh)12(PEt3)8][PEt3Ph] 5, and [Cu39Te16(TePh)11(PEt3)13] 6
1
2
3
4
5
6
chemical formula
C24H46P4Cu2Te2 C51H83P3Cu4Te4 [C54H75P3Cu5Te6] C72H120P6Cu12Te9 [C120H180Cu29P8Te21] C144H250P13Cu39Te27
[C12H20P]
2095.60
[C12H20P]
6587.91
-73
formula weight
temperature (°C)
space group
a (Å)
840.77
1553.64
3082.38
8307.31
-73
-73
-73
-73
-73
P21/c (No. 14)
17.528(4)
13.891(3)
13.882(3)
P21/n (No. 14)
11.701(1)
20.502(2)
25.555(3)
P21/c (No. 14)
17.480(1)
14.552(1)
30.403(2)
P 3h1c (No. 163)
15.345(1)
P21 (No.4)
19.830(3)
18.193(2)
30.101(4)
P 1h (No. 1)
19.6195(2)
20.6286(3)
32.1288(5)
87.518(8)
88.547(8)
64.092(8)
11704.8
b (Å)
c (Å)
24.412(2)
R (deg)
â (deg)
90.45(3)
102.299(9)
91.99(1)
100.28(2)
γ (deg)
V (Å3)
3379.9
3.151
4
5989.8
7728.9
4978.1
10685(3)
5.726
µ (Mo KR1, mm-1
Z
)
3.421
3.691
5.221
6.887
4
4
2
2
2
Fc (g cm-3
)
1.652
1.723
1.801
2.056
2.048
2.357
R indices [I > 2σ(I)]a R1 ) 0.0394
wR2 ) 0.1067
R1 ) 0.0288
R1 ) 0.0470
R1 ) 0.0561
R1 ) 0.0836
R1 ) 0.0644
wR2 ) 0.0747
wR2 ) 0.1068
wR2 ) 0.1445
wR2 ) 0.2236
wR2 ) 0.1491
a R1 ) ∑||Fo| - |Fc||/∑|Fo|. wR2 ) {∑[w(Fo - Fc2)2/∑[wFo ]2}1/2
.
2
2
Scheme 1
X-ray Analyses. The selection and mounting of single crystals
suitable for X-ray diffraction were carried out by immersing the air-
sensitive samples in perfluoropolyetheroil (Riedel de Ha¨en) and
mounting the coated crystal on a glass pin set in a goniometer head,
the oil setting upon cooling in a flow of N2. Data were collected on
either a Nonius Kappa-CCD diffractometer using COLLECT (Nonius,
1998) software (6) or on a STOE IPDS instrument (1-5) equipped
with an imaging plate area detector and a rotating anode. Data were
corrected for Lorentz and polarization effects. The SHELXTL (G. M.
Sheldrick, Madison, WI) program package was used to solve (direct
methods, Cu and Te) and refine the structures. The weighting scheme
employed was of the form w ) 1/[σ2(Fo ) + (a‚P)2 + b‚P] (a, b )
2
1
2
2
refined variables, P ) /3max(Fo , 0) + /3 Fc2). All structures solved
and refined without complications, with the following exceptions:
complex 1 was satisfactorily solved and refined in the monoclinic space
group P2(1)/c with two crystallographically independent (half) mol-
ecules in the asymmetric unit. Due to the similarity of the lengths of
axes b and c and the small value of the angle beta, attempts were made
to solve the structure in higher symmetry however these were not
successful, as evidenced by the high R(int) (eg. orthorhombic R(int)
) 53%). In complex 3, the ligand P3, the ethyl chains about atoms P1
and P2 and phenyl rings about Te4, Te5, and Te6 were all disordered
and a two-site model was satisfactorily refined with 60:40 occupancy.
For cluster 4, a similar two-site model was refined for atoms C1-C6
(50:50 occupancy) and atoms C7-C12 (70:30). Disordered C atoms
were refined isotropically. In cluster 6, atom Te4 was refined aniso-
tropically over two sites with 50:50 occupancy. Complete details of
these site disorders are contained in the Supporting Information. A
summary of the X-ray determinations is given in Table 1. Figures of
complexes 3-6 were generated using the Schakal program.11
yield (Scheme 1). The molecular structure of 1 is illustrated in
Figure 1 and selected bond lengths and angles are listed in Table
2. Cluster 1 crystallizes in the monoclinic space group P2(1)/c
with two independent molecules in the asymmetric unit, each
of which resides on a crystallographic inversion center. Although
chemically identical, there are marked differences in some of
the related bond lengths and angles of the two molecules,
illustrating the coordination flexibility of the phenyltellurolate
ligands. The Cu centers display pseudo tetrahedral coordination
geometry ( range from 101.1(1)-121.88(4)°) via a combina-
tion of two phosphorus and two tellurium ligands. The µTe-
Cu bond distances are similar in both molecules (2.6353(8),
2.6676(7) Å molecule 1; 2.6316(7), 2.6673(9) Å molecule 2)
and are typical for bridging tellurolate complexes.6 The geometry
about the Te centers in the two molecules differs significantly.
In molecule 1, the angle Cu11-Te11-Cu11A is 63.90(2)°
whereas it is 71.63(2)° in molecule 2. This is accompanied with
an increase in the nonbonding Cu(I)‚‚‚Cu(I) distance from 2.806-
(1) Å in molecule 1 to 3.101(1) Å in molecule 2 and a
concomitant rotation of the phenyl rings. Thus in molecule 1,
the two trans rings line up along the vectors Cu12-Te12 and
Cu1B-Te1B respectively, (dihedral angle between planes
defined by Cu11-Te11-C11 and Te11-C11-C21 ) 2.4°)
whereas they are rotated (23.3°) in molecule 2. It is interesting
to note that the Cu2Te2 arrangements in both molecules of 1
are planar whereas a puckered, butterfly geometry has been
reported for the sterically crowded complex {Cu[SeC(SiMe3)3]-
PCy3}2.12 Oliver et al.13 have reported a similar Cu2Se2 frame
with the electrochemical preparation of [Ph3PCu(µ-SePh)2Cu-
(PPh3)2] that contains both three- and four-coordinate copper
Results and Discussion
Synthesis and Structural Characterization. The use of
silyltelluroether reagents offers a facile route into metal-
tellurium polynuclear complexes. The -SiMe3 moiety is
eliminated readily from the main group metal center when
treated with transition metal salts (eq 1).
LnM-X + Te(Ph)SiMe3 f LnM-TeR + XSiMe3 (1)
Thus when CuCl is dissolved in THF with PMe3 and treated
with Te(Ph)SiMe3, [Cu2(µ-TePh)2(PMe3)4] 1 is isolated in good
(10) Noviandri, I.; Brown, K. N.; Fleming, D. S.; Gulyas, P. T.; Lay, P.
A.; Masters, A. F.; Phillips, L. J. Phys. Chem. B 1999, 103, 6713-
6722.
(11) Keller, E. SCHAKAL 1999, A Computer Program for the Graphic
Representation of Molecular and Crystallographic Models; Universita¨t
Freiburg, 1999.
(12) Bonasia, P. J.; Mitchell, G. P.; Hollander, F. J.; Arnold, J. Inorg. Chem.
1994, 33, 1797-1802.

Copper-Phenyltellurolate Complexes
Inorganic Chemistry, Vol. 40, No. 18, 2001 4681
Figure 1. The molecular structure of [Cu2(µ-TePh)2(PMe3)4] 1, illustrating the two crystallographically independent molecules. Thermal parameters
are drawn at the 40% probability level.
Table 2. Selected Bond Lengths (Å) and Angles (deg) for [Cu2(µ-TePh)2(PMe3)4] 1, [Cu4(µ-TePh)4(PPri3)3] 2, [Cu5(TePh)6(PEt3)3][PEt3Ph] 3,
and [Cu12Te3(TePh)6(PEt3)6] 4
molecule 1
molecule 2
[Cu2(µ-TePh)2(PMe3)4] 1
Te(11)-C(11)
2.131(4)
Te(12)-C(12)
2.128(4)
Te(11)-Cu(11)
Te(11)-Cu(1A)
Cu(11)-P(11)
Cu(11)-P(21)
Cu(11)-Te(1A)
2.6353(9)
2.6677(7)
2.2705(13)
2.2705(11)
2.6677(7)
Te(12)-Cu(12)
Te(12)-Cu(1B)
Cu(12)-P(22)
Cu(12)-P(12)
Cu(12)-Te(1B)
2.6316(7)
2.6672(9)
2.2577(11)
2.2584(13)
2.6672(9)
Cu(11)-Cu(1A)
2.8063(10)
107.72(11)
101.10(10)
109.48(5)
121.88(4)
98.38(4)
99.23(4)
112.13(4)
116.10(2)
C(12)-Te(12)-Cu(12)
C(12)-Te(12)-Cu(1B)
Cu(12)-Te(12)-Cu(1B)
P(22)-Cu(12)-P(12)
P(22)-Cu(12)-Te(12)
P(12)-Cu(12)-Te(12)
P(22)-Cu(12)-Te(1B)
P(12)-Cu(12)-Te(1B)
Te(12)-Cu(12)-Te(1B)
107.41(11)
103.09(11)
71.632(19)
110.68(4)
123.83(4)
101.28(3)
100.78(4)
112.11(4)
108.368(19)
C(11)-Te(11)-Cu(11)
C(11)-Te(11)-Cu(1A)
P(11)-Cu(11)-P(21)
P(11)-Cu(11)-Te(11)
P(21)-Cu(11)-Te(11)
P(11)-Cu(11)-Te(1A)
P(21)-Cu(11)-Te(1A)
Te(11)-Cu(11)-Te(1A)
[Cu4(µ-TePh)4(PPri3)3] 2
Te(1)-C(1)
Te(1)-Cu(1)
Te(1)-Cu(3)
Te(1)-Cu(4)
Te(2)-C(7)
Te(2)-Cu(2)
Te(2)-Cu(1)
Te(2)-Cu(4)
Te(3)-C(13)
Te(3)-Cu(2)
Te(3)-Cu(3)
2.124(4)
Te(3)-Cu(4)
Te(4)-C(19)
Te(4)-Cu(4)
Te(4)-Cu(3)
Te(4)-Cu(1)
Cu(1)-P(1)
Cu(1)-Cu(4)
Cu(2)-P(2)
Cu(2)-Cu(4)
Cu(3)-P(3)
Cu(3)-Cu(4)
2.6510(6)
2.132(5)
2.6251(6)
2.6254(6)
2.8420(6)
2.124(4)
2.5734(6)
2.6060(6)
2.6680(6)
2.127(5)
2.5554(6)
3.0557(7)
3.1484(7)
2.2210(12)
2.4843(7)
2.2282(12)
2.5337(7)
2.2333(11)
2.4822(7)
2.5960(6)
2.6375(6)
[Cu5(TePh)6(PEt3)3][PEt3Ph] 3
Te(1)-Cu(1)
Te(1)-Cu(2)
Te(2)-Cu(1)
Te(2)-Cu(3)
Te(3)-Cu(1)
Te(3)-Cu(4)
Te(6)-Cu(5)
Te(6)-Cu(2)
Te(6)-Cu(4)
Cu(1)-Cu(5)
2.5639(13)
2.6100(15)
2.5365(14)
2.6352(14)
2.4889(15)
2.6463(17)
2.6235(13)
2.6497(17)
2.6595(16)
2.8909(18)
Te(4)-Cu(5)
Te(4)-Cu(3)
Te(4)-Cu(2)
Te(5)-Cu(5)
Te(5)-Cu(3)
Te(5)-Cu(4)
Cu(2)-Cu(5)
Cu(3)-Cu(5)
Cu(4)-Cu(5)
2.6435(15)
2.6599(13)
2.6600(15)
2.6227(12)
2.6473(14)
2.6626(14)
2.5869(15)
2.6040(17)
2.6132(19)
[Cu12Te3(TePh)6(PEt3)6] 4
Te(1)-Cu(1A)
Te(1)-Cu(2)
Te(1)-Cu(1)
2.6270(13)
2.6348(11)
2.6650(14)
Te(2)-Cu(2A)
Te(2)-Cu(2)
Te(2)-Cu(1)
2.6066(11)
2.6550(12)
2.7690(12)

4682 Inorganic Chemistry, Vol. 40, No. 18, 2001
DeGroot et al.
Figure 3. The molecular structure of the anionic cluster [Cu5(TePh)6-
(PEt3)3]- 3. Carbon atoms about the phosphorus centers and hydrogen
atoms have been omitted for clarity.
Figure 2. The molecular structure of [Cu4(µ-TePh)4(PPri3)3] 2. Thermal
parameters are drawn at the 40% probability level. Hydrogen atoms
and carbon atoms bonded to the phosphorus centers have been omitted
for clarity.
centers with both phenyl rings of the selenolate ligands lying
to the same side of the Cu2Se2 plane, as observed in [(Ph3P)2-
Cu(µ-SPh)2Cu(PPh3)2].14
A similar reaction for the synthesis of 1 with the larger
phosphine15 PPri3 in diethyl ether leads to the tetranuclear cluster
molecule [Cu4(µ3-TePh)4(PPri3)3] 2 (Figure 2, Scheme 1). Unlike
in 1 where the Cu centers are both four-coordinate, the copper
sites in 2 are best described as trigonal planar, with Cu1, Cu3,
and Cu4 all displaying a fourth, long contact to tellurium centers
(Table 2). The overall geometry of the CuTe core is such that
Cu1 and Cu3 asymmetrically cap two faces of the nonbonded
Te4 tetrahedron while Cu2 bridges a Te‚‚‚Te edge and the only
Cu center not bonded to a phosphine ligand (Cu4) lying slightly
below a Te3 face.
An examination of the bonding contacts for the Cu sites in 2
illustrates two symmetrical Cu-Te bonds for (Pri3P)Cu2 (Cu2-
Te2 ) 2.573(1); Cu2-Te3 ) 2.596(1) Å) whereas the other
two phosphine bonded centers (Cu1 and Cu3) display two
shorter Cu-Te bonds (Cu1-Te1 ) 2.625(1); Cu1-Te2 )
2.606(1); Cu3-Te1 ) 2.625(1); Cu3-Te3 ) 2.638(1) Å) and
a markedly long contact to Te4 (Cu1-Te4 ) 3.148(1); Cu3-
Te4 ) 3.056(1) Å). Indeed, the phenyltellurolate ligand Te4 is
perhaps best described as “pseudo-terminal” with an exception-
ally short Te4-Cu4 bonding distance of 2.555(1) Å. The three
additional Cu-Te contacts (Cu4-Te1 ) 2.842(1); Cu4-Te2
) 2.668(1); Cu4-Te3 ) 2.651(1) Å) are also longer than the
former.
Unlike the preparation of 1 and 2, it did not prove possible
to isolate phosphine-stabilized copper-tellurolate complexes
with PEt3 and ethereal solvents, the reaction mixtures invariably
producing oily residues. Carrying out the reaction in a less polar
solvent (pentane) however, lead to the isolation of [Cu5(µ-
TePh)3(µ3-TePh)3(PEt3)3][PEt3Ph] 3 and [Cu12Te3(µ3-TePh)6-
(PEt3)6] 4 in modest yields (Scheme 1), as the two clusters
cocrystallized from the reaction mixture upon standing. The
molecular structures of 3 and 4 are illustrated in Figures 3 and
4, respectively. The anionic cluster 3 is comprised of six
phenyltellurolate groups and five copper(I) centers, with the
Figure 4. The molecular structure of [Cu12Te3(TePh)6(PEt3)6] 4
(hydrogen atoms omitted).
[PEt3Ph]+ cation arising from free phosphine and a phenyl group
from TePh centers, as has been observed previously.6
In 3 there are three µ2- (Te1, Te2, Te3) and three µ3-TePh
(Te4, Te5, Te6) ligands defining a distorted octahedral array,
with the three PEt3 bonded Cu centers (Cu2-Cu4) each lying
above a deltahedral face. The two remaining three-coordinate
Cu centers (Cu1 and Cu5) are both symmetrically bonded to
three tellurium ligands (Cu1-Te, 2.489(2)-2.564(1); Cu5-Te,
2.624(1)-2.643(2) Å) with the µ2-Te-Cu contacts shorter than
their µ3 counterparts. Unlike in 1, where the µ3-TePh ligands
make two shorter and one longer Te-Cu contacts, the three
µ3-Te(Ph)-Cu bonds are much more symmetric (Cu-Te, 2.629-
(2)-2.663(2) Å). The smaller PEt3 ligands (vs PPri3) in 3 thus
result in a slightly distorted tetrahedral coordination geometry
for Cu2-Cu4, with three roughly equal Cu-Te bond lengths
(Table 2). The structure of cluster 3 is closely related to that
reported for the neutral complex [Cu6(TePh)6(PEtPh2)5], with
the “additional” Cu(PR3)2 center bonded to Te1 and Te3.6
The second cluster generated with CuCl‚PEt3, dark green
crystals of [Cu12Te3(µ3-TePh)6(PEt3)6] 4, consists of twelve Cu-
(I) centers bonded to six µ3-Te(Ph)- and three µ6-Te2- ligands
(Figure 4, Table 2), the latter arising from the light-induced
generation of TePh2 in the reaction mixture. Indeed, if the
reaction is carried in the absence of visible light, clusters 3 and
4 do not form. The structure of 4 is virtually identical to that
(13) Kampf, J.; Kumar, R.; Oliver, J. P. Inorg. Chem. 1992, 31, 3626-
3629.
(14) Dance, I. G.; Guerney, P. J.; Rae, A. D.; Scudder, M. L. Inorg. Chem.
1983, 22, 2883-2887.
(15) Tolmann, C. A. Chem. ReV. 1977, 77, 313-348.

Copper-Phenyltellurolate Complexes
Inorganic Chemistry, Vol. 40, No. 18, 2001 4683
Table 3. Selected Bond Lengths (Å) for
[Cu29Te9(TePh)12(PEt3)8][PEt3Ph] 5
Te(1)-Cu(4)
2.554(4)
2.661(6)
2.687(5)
2.563(4)
2.628(5)
2.683(5)
2.588(4)
2.595(4)
2.641(4)
2.561(4)
2.632(4)
2.642(4)
2.644(5)
2.647(4)
2.662(4)
2.606(4)
2.606(4)
2.642(5)
2.560(4)
2.622(4)
2.657(5)
2.625(5)
2.652(5)
2.669(4)
2.591(4)
2.621(5)
2.665(5)
2.623(4)
2.681(5)
2.732(5)
2.838(4)
2.594(4)
2.641(5)
2.645(5)
2.619(4)
2.682(5)
2.723(5)
2.843(4)
2.548(3)
2.580(5)
2.736(4)
2.759(4)
2.838(5)
2.770(4)
3.061(4)
2.563(4)
2.568(4)
2.640(4)
2.664(4)
2.773(5)
2.822(5)
2.577(4)
Te(13)-Cu(8)
Te(13)-Cu(10)
Te(13)-Cu(3)
Te(14)-Cu(18)
Te(14)-Cu(1)
Te(14)-Cu(12)
Te(14)-Cu(10)
Te(14)-Cu(13)
Te(14)-Cu(15)
Te(14)-Cu(11)
Te(14)-Cu(4)
Te(15)-Cu(8)
Te(15)-Cu(10)
Te(15)-Cu(4)
Te(15)-Cu(22)
Te(15)-Cu(20)
Te(15)-Cu(2)
Te(15)-Cu(12)
Te(16)-Cu(13)
Te(16)-Cu(11)
Te(16)-Cu(3)
Te(16)-Cu(21)
Te(16)-Cu(23)
Te(16)-Cu(5)
Te(16)-Cu(9)
Te(17)-Cu(20)
Te(17)-Cu(6)
Te(17)-Cu(16)
Te(17)-Cu(26)
Te(17)-Cu(24)
Te(17)-Cu(17)
Te(17)-Cu(8)
Te(18)-Cu(16)
Te(18)-Cu(21)
Te(18)-Cu(9)
Te(18)-Cu(24)
Te(18)-Cu(27)
Te(18)-Cu(7)
Te(19)-Cu(23)
Te(19)-Cu(15)
Te(19)-Cu(25)
Te(19)-Cu(19)
Te(19)-Cu(29)
Te(21)-Cu(17)
Te(21)-Cu(22)
Te(21)-Cu(21)
Te(21)-Cu(20)
Te(21)-Cu(23)
Te(21)-Cu(24)
Te(21)-Cu(11)
Te(21)-Cu(25)
Te(21)-Cu(10)
2.886(5)
2.918(4)
3.080(5)
2.548(3)
2.569(5)
2.704(4)
2.730(4)
2.806(4)
2.896(5)
3.040(4)
3.074(5)
2.555(4)
2.633(4)
2.686(4)
2.741(4)
2.794(4)
2.811(4)
2.949(4)
2.583(4)
2.612(4)
2.640(4)
2.724(4)
2.761(4)
2.808(5)
3.034(4)
2.597(4)
2.679(4)
2.719(4)
2.728(4)
2.750(4)
2.765(4)
3.061(4)
2.562(4)
2.585(4)
2.622(4)
2.673(4)
2.790(4)
2.804(4)
2.580(4)
2.684(4)
2.707(4)
2.720(4)
2.724(4)
2.589(4)
2.720(4)
2.739(4)
2.860(4)
2.860(4)
3.001(4)
3.035(4)
3.093(4)
3.135(4)
Te(1)-Cu(1)
Te(1)-Cu(2)
Te(2)-Cu(3)
Te(2)-Cu(1)
Te(2)-Cu(5)
Te(3)-Cu(6)
Te(3)-Cu(8)
Te(3)-Cu(2)
Te(4)-Cu(6)
Te(4)-Cu(16)
Te(4)-Cu(7)
Te(5)-Cu(3)
Te(5)-Cu(7)
Te(5)-Cu(9)
Te(6)-Cu(13)
Te(6)-Cu(15)
Te(6)-Cu(5)
Figure 5. The molecular structure of [Cu29Te9(TePh)12(PEt3)8]-
5
Te(7)-Cu(15)
Te(7)-Cu(19)
Te(7)-Cu(14)
Te(8)-Cu(4)
(carbon atoms omitted). For clarity the copper centers are labeled with
numbers only. Phenyltellurolate ligands are labeled Te1-Te12.
Te(8)-Cu(14)
Te(8)-Cu(12)
Te(9)-Cu(24)
Te(9)-Cu(27)
Te(9)-Cu(26)
Te(10)-Cu(23)
Te(10)-Cu(27)
Te(10)-Cu(29)
Te(10)-Cu(21)
Te(11)-Cu(25)
Te(11)-Cu(29)
Te(11)-Cu(28)
Te(12)-Cu(20)
Te(12)-Cu(28)
Te(12)-Cu(26)
Te(12)-Cu(22)
Te(13)-Cu(17)
Te(13)-Cu(1)
Te(13)-Cu(9)
Te(13)-Cu(11)
Te(13)-Cu(6)
Te(19)-Cu(18)
Te(19)-Cu(13)
Te(20)-Cu(19)
Te(20)-Cu(22)
Te(20)-Cu(12)
Te(20)-Cu(25)
Te(20)-Cu(28)
Te(20)-Cu(14)
Te(21)-Cu(18)
Figure 6. A space filling representation of [Cu29Te9(TePh)12(PEt3)8][PEt3-
Ph] 5.
already described for [Cu12Te3(µ3-TePh)6(PPh3)6]6 and need not
be discussed further here.
Although the solubility of clusters 3 and 4 is limited in
hydrocarbon solvents, both are freely soluble in tetrahydrofuran.
When a 1:1.5 molar mixture of 3:4 is photolyzed (λ cutoff )
320 nm), the reaction mixture gradually darkens to a wine color,
and when this is layered with diethyl ether, hair-like crystals of
[Cu29Te9(µ3-TePh)10(µ4-TePh)2(PEt3)8][PEt3Ph] 5 form in 42%
yield. The molecular structure of 5 is illustrated in Figure 5.
The highly condensed cluster consists of 29 trigonal planar and
tetrahedral copper(I) centers. The bonding contacts for 5 are
typical for Cu-Te clusters and are summarized in Table 3.
Twelve Ph groups and the eight PEt3 ligands solubilize the Cu29-
Te21 core, as illustrated with a space-filling model in Figure 6.
Indeed, it would appear that the anionic nature of the cluster
aids in rendering it much more soluble in THF than related,
neutral CuTe complexes.16,18 With good solubility in THF, it
proved possible to explore the electrochemical behavior of 5
(vide infra). The Te21 framework in 5 is virtually identical to
that reported for the neutral, silver-tellurium cluster [Ag30-
(TePh)12Te9(PEt3)12], that can be synthesized from Et3P‚AgCl
and a combination of Te(SiMe3)2 and Te(Ph)SiMe3.17 The
synthesis of 5 from the co-condensation of 3 and 4 arises, in
part, from the elimination of TePh2 that can be isolated from
the reaction mixture. Although it may be easy to view this
reaction as a “2 × 12 Cu + 5 Cu” yields 29 Cu in 5, the
formation of small amounts of brown crystals of [Cu39(µ3-
TePh)10(µ4-TePh)Te16(PEt3)13] 6 from the synthesis of 5 pre-
cludes such an oversimplification. The molecular structure of
cluster 6 is shown in Figure 7 and a selection of bond lengths
is listed in Table 4.
The structure of the copper-telluride cluster 6 is perhaps best
described as being related to that of 5 that has undergone
“skeletal expansion”. Although there are but 11 Te(Ph)-
moieties in 6 (vs12 in 5), there are 16 Te2- centers distributed
in the cluster core. The latter Te sites are arranged to yield a
(nonbonded) tri-capped centered icosahedron (Figure 8), such
deltahedral arrangements a common characteristic of high-
nuclearity, spherical [CuxTey(PR3)z] clusters.18 Also similar to
such Cu-Te condensed systems, the Cu:Te:Te(Ph) ratio in 6
is such that it is not possible to assign a +1 oxidation state to
the copper centers. Noteworthy with the structures of the
(16) Semmelmann, M.; Fenske, D.; Corrigan, J. F. J. Chem. Soc., Dalton
Trans. 1998, 2541-2545.
(17) Corrigan, J. F.; Fenske, D. Chem. Commun. 1997, 1837-1838.
(18) Corrigan, J. F, Balter, S.; Fenske, D. J. Chem. Soc., Dalton Trans.
1996, 729-738.

4684 Inorganic Chemistry, Vol. 40, No. 18, 2001
DeGroot et al.
Table 4. Selected Bond Lengths (Å) for [Cu39(TePh)11Te16(PEt3)13] 6
Te(1)-Cu(4)
Te(1)-Cu(6)
Te(1)-Cu(8)
Te(2)-Cu(7)
Te(2)-Cu(3)
Te(2)-Cu(2)
Te(3)-Cu(5)
Te(3)-Cu(3)
Te(3)-Cu(1)
Te(4)-Cu(17)
Te(4)-Cu(11)
Te(4)-Cu(4)
Te(5)-Cu(22)
Te(5)-Cu(11)
Te(5)-Cu(15)
Te(6)-Cu(26)
Te(6)-Cu(14)
Te(6)-Cu(21)
Te(7)-Cu(20)
Te(7)-Cu(8)
Te(7)-Cu(14)
Te(8)-Cu(28)
Te(8)-Cu(31)
Te(8)-Cu(37)
Te(8)-Cu(38)
Te(9)-Cu(33)
Te(9)-Cu(37)
Te(9)-Cu(34)
Te(10)-Cu(32)
Te(10)-Cu(29)
Te(10)-Cu(39)
Te(11)-Cu(36)
Te(11)-Cu(35)
Te(11)-Cu(38)
Te(12)-Cu(6)
Te(12)-Cu(10)
2.5648(16)
2.6326(16)
2.6859(17)
2.6379(15)
2.6395(17)
2.6922(17)
2.6195(16)
2.6362(17)
2.6887(16)
2.6349(16)
2.6459(17)
2.6793(17)
2.6336(16)
2.6643(17)
2.6875(15)
2.6194(15)
2.6654(16)
2.6780(17)
2.6057(16)
2.6696(17)
2.6794(17)
2.6561(16)
2.6792(15)
2.7056(17)
2.7193(17)
2.6417(15)
2.6470(16)
2.6477(15)
2.6398(16)
2.6431(17)
2.6563(19)
2.6219(17)
2.6367(15)
2.6553(17)
2.5871(16)
2.6779(16)
Te(13)-Cu(9)
Te(13)-Cu(1)
Te(13)-Cu(12)
Te(13)-Cu(5)
Te(14)-Cu(19)
Te(14)-Cu(21)
Te(14)-Cu(10)
Te(14)-Cu(2)
Te(14)-Cu(13)
Te(14)-Cu(7)
Te(15)-Cu(5)
Te(15)-Cu(7)
Te(15)-Cu(19)
Te(15)-Cu(16)
Te(15)-Cu(24)
Te(15)-Cu(3)
Te(16)-Cu(6)
Te(16)-Cu(23)
Te(16)-Cu(9)
Te(16)-Cu(18)
Te(16)-Cu(17)
Te(16)-Cu(22)
Te(16)-Cu(15)
Te(16)-Cu(4)
Te(17)-Cu(25)
Te(17)-Cu(6)
Te(17)-Cu(18)
Te(17)-Cu(10)
Te(17)-Cu(20)
Te(17)-Cu(26)
Te(17)-Cu(21)
Te(18)-Cu(23)
Te(18)-Cu(25)
Te(18)-Cu(9)
Te(18)-Cu(24)
Te(18)-Cu(10)
2.6440(16)
2.6901(16)
2.7679(15)
3.0017(16)
2.5494(16)
2.5570(16)
2.6563(15)
2.7112(16)
2.7321(16)
2.8059(17)
2.5542(15)
2.6001(16)
2.6541(17)
2.6823(15)
2.7776(16)
2.8433(16)
2.6023(15)
2.6350(15)
2.6663(15)
2.6882(17)
2.7831(16)
2.7980(15)
2.8121(16)
2.9071(17)
2.6351(15)
2.6481(17)
2.6613(16)
2.6786(16)
2.7022(16)
2.7565(17)
2.8285(16)
2.6463(14)
2.6547(16)
2.6548(15)
2.6634(15)
2.6685(15)
Te(12)-Cu(9)
Te(12)-Cu(2)
Te(12)-Cu(5)
Te(12)-Cu(1)
Te(12)-Cu(7)
Te(13)-Cu(16)
Te(13)-Cu(15)
Te(19)-Cu(31)
Te(19)-Cu(8)
Te(19)-Cu(28)
Te(19)-Cu(17)
Te(20)-Cu(24)
Te(20)-Cu(27)
Te(20)-Cu(12)
Te(20)-Cu(16)
Te(20)-Cu(29)
Te(20)-Cu(32)
Te(21)-Cu(24)
Te(21)-Cu(30)
Te(21)-Cu(19)
Te(21)-Cu(13)
Te(21)-Cu(32)
Te(21)-Cu(29)
Te(22)-Cu(33)
Te(22)-Cu(22)
Te(22)-Cu(28)
Te(22)-Cu(17)
Te(22)-Cu(37)
Te(22)-Cu(11)
Te(23)-Cu(23)
Te(23)-Cu(34)
Te(23)-Cu(15)
Te(23)-Cu(12)
Te(23)-Cu(27)
Te(23)-Cu(22)
Te(23)-Cu(33)
2.6813(15)
2.7348(16)
2.7799(16)
2.7881(17)
2.9170(16)
2.5468(15)
2.5594(15)
2.7365(16)
2.7586(17)
2.7610(16)
2.7778(17)
2.5771(16)
2.5975(16)
2.6880(15)
2.7012(15)
2.7464(17)
3.0624(19)
2.5827(16)
2.6059(15)
2.6455(15)
2.7041(16)
2.7289(16)
2.9604(18)
2.5534(14)
2.6040(15)
2.6055(16)
2.6163(15)
2.8246(16)
2.8254(16)
2.6312(15)
2.6540(17)
2.6700(16)
2.7161(16)
2.7357(15)
2.8180(15)
2.9078(16)
Te(18)-Cu(27)
Te(18)-Cu(30)
Te(18)-Cu(19)
Te(18)-Cu(16)
Te(19)-Cu(4)
Te(19)-Cu(18)
Te(19)-Cu(20)
Te(24)-Cu(25)
Te(24)-Cu(36)
Te(24)-Cu(21)
Te(24)-Cu(13)
Te(24)-Cu(30)
Te(24)-Cu(35)
Te(24)-Cu(26)
Te(25)-Cu(35)
Te(25)-Cu(31)
Te(25)-Cu(26)
Te(25)-Cu(20)
Te(25)-Cu(14)
Te(25)-Cu(38)
Te(26)-Cu(25)
Te(26)-Cu(23)
Te(26)-Cu(18)
Te(26)-Cu(33)
Te(26)-Cu(28)
Te(26)-Cu(31)
Te(26)-Cu(36)
Te(26)-Cu(35)
Te(26)-Cu(34)
Te(27)-Cu(32)
Te(27)-Cu(36)
Te(27)-Cu(34)
Te(27)-Cu(27)
Te(27)-Cu(30)
Te(27)-Cu(39)
2.7936(16)
2.8159(16)
3.0011(16)
3.0035(17)
2.6737(17)
2.6786(16)
2.7130(16)
2.6439(16)
2.6517(16)
2.6570(16)
2.6807(16)
2.7003(17)
2.8712(16)
2.8851(16)
2.5626(16)
2.5813(16)
2.5837(15)
2.7397(17)
2.7992(16)
2.8055(17)
2.6444(15)
2.6453(16)
2.6866(16)
2.7950(16)
2.8096(15)
2.8098(17)
2.8176(17)
2.8242(17)
2.8432(16)
2.5412(16)
2.5432(17)
2.5432(15)
2.7381(17)
2.7418(15)
2.7588(17)
Figure 8. The (nonbonded) Te framework of the telluride ligands in
6.
Figure 7. The molecular structure of the [Cu39(TePh)11Te16(PEt3)13] 6
(carbon atoms omitted). For clarity the copper centers are labeled with
numbers only. Phenyltellurolate ligands are labeled Te1-Te11.
nanoclusters 5 and 6 is that they bear no resemblance to those
reported for triethylphosphine/alkyltellurolate/telluride/copper
clusters,18,19 clearly demonstrating the effect that the carbon
substituents on tellurium exert on controlling product formation.
UV-Vis Spectroscopy and Cyclic Voltammetry. The UV-
vis solution spectrum of 5 in THF displays a broad featureless
absorption, with an onset of ∼520 nm and no discernible
maximum (Figure 9). The solid-state (diffuse reflectance, in
KBr) spectrum displays a similar profile, although there is a
weak maximum observed at ∼570 nm. The solution spectrum
Figure 9. Solution and solid-state (diffuse reflectance) UV-vis spectra
for 5 and 6.
for 6 is similar to that observed for 5 (Figure 9) with an onset
of absorption at λ ∼ 600 nm. The diffuse reflectance spectrum
UV-vis spectrum of 6 in KBr shows an additional feature, with
(19) Fenske, D.; Zhu, N. Y. J. Cluster Sci. 2000, 11, 135-151.

Copper-Phenyltellurolate Complexes
Inorganic Chemistry, Vol. 40, No. 18, 2001 4685
oxidation of the neutral complex to the corresponding cation.
The standard potentials of these two processes are -1.02 and
-0.64 (0.01 V versus the ferrocene/ferrocinium redox couple,
respectively. Attempts to isolate either of the two oxidized
species using appropriate counterions have yet to prove suc-
cessful. While the neutral complex is stable under these
conditions over the time scale of the experiment, the loss of
some of the chemical reversibility of the cation at slower scan
rates suggests that there is a competing chemical process that
is occurring.
Conclusions
A series of trialkylphosphine-stabilized copper-tellurolate
cluster complexes has been prepared using the silylated reagent
Te(Ph)SiMe3. We have shown that controlled condensation of
low nuclearity clusters can be achieved using photolysis to
promote the elimination of TePh2, leading to the generation of
nanometer sized copper-tellurium frameworks.
Figure 10. The cyclic voltammogram for 5 in THF (1 mM) with 0.1
M [NBu4][BF4] (100 mV/s).
a clearly defined absorption band at 520 nm. Similar absorption
profile characteristics have been reported recently for high-
nuclearity copper telluride clusters, and the lower energy bands
have been attributed to the delocalized bonding in such
nanometer sized particles.2a
The good solubility of the anion 5 permitted an electrochemi-
cal analysis to be performed. An electrochemical cell was
prepared by dissolving 1 or 2 mM Cu29 in dry THF containing
0.1-0.2 M [Bu4N][BF4] as an electrolyte, to give a red-wine
solution. A three-electrode setup was used as described in the
Experimental Section. Cyclic voltammograms (CV’s) were
obtained by scanning between -1 to 0.8 V at scan rates varying
from 0.05 V/s to 0.5 V/s. Figure 10 shows a representative CV
measured at 0.2 V/s showing two single electron processes that
are chemically reversible on these time scales. These redox
processes are assigned to the reversible anodic oxidation of
[Cu29]- to the neutral Cu29 complex and subsequent further
Acknowledgment. We are grateful to the Natural Sciences
and Engineering Research Council of Canada and the University
of Western Ontario’s ADF program for supporting this research.
Dr. Nicholas J. Taylor (University of Waterloo, Canada) is
thanked for discussions regarding the X-ray refinement of 5.
We also acknowledge the Canada Foundation for Innovation
and the Ontario Research and Development Challenge Fund for
equipment funding. J.F.C. thanks Prof. Dieter Fenske (Univer-
sita¨t Karlsruhe) for providing access to facilities for X-ray data
collection.
Supporting Information Available: X-ray crystallographic files
in CIF format for the structure determinations of 1-6. This material is
available free of charge via the Internet at http://pubs.acs.org.
IC001260K