ic001260k_si_001.cif (246.12 kB)

Trialkylphosphine-Stabilized Copper−Phenyltellurolate Complexes:  From Small Molecules to Nanoclusters via Condensation Reactions

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posted on 27.07.2001, 00:00 by Marty W. DeGroot, Michael W. Cockburn, Mark S. Workentin, John F. Corrigan
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, [Cu43-TePh)4(PPri3)3] 2, [Cu5(μ-TePh)33-TePh)3(PEt3)3][PEt3Ph] 3, and [Cu12Te33-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 [Cu29Te93-TePh)104-TePh)2(PEt3)8][PEt3Ph] 5 in good yield, in addition to small amounts of [Cu393-TePh)104-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.