Table of Contents
Metal-Based Drugs
Volume 6, Issue 4-5, Pages 255-260
http://dx.doi.org/10.1155/MBD.1999.255

Electronic Structure of Dinuclear Gold(I) Complexes

1University of Maine, Department.of Chemistry, Orono 04469-5706, Maine, USA
2Brandeis University, Waltham 02454-9110, MA, USA

Received 14 December 1998; Accepted 19 February 1999

Copyright © 1999 Hindawi Publishing Corporation. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Abstract

Cyclic voltammetry (CV) experiments on LL(AuSR)2 complexes [LL = diphenylphosphinomethane (dppm), diphenylphosphinopentane (dpppn); R* = p-SC6H4CH3] show anodic sweeps that broaden by about 25 mV on going from the longer (dpppn) to the shorter (dppm) bidentate phosphine ligand. Changing concentrations had no effect on the shape of the waveform. The result suggests a weak intramolecular metal-metal interaction in dppm(AuSR)2 that correlates well with rate acceleration occurring in the reaction of dppm(AuSR)2 with organic disulfides. Quantum yields for cis-dppee(AuX)2 [dppee = 1,2-bis(diphenylphosphino)ethylene; X = Cl, Br, I] complexes, (disappearance)Φ, are significantly higher in complexes with a softer X ligand, a trend that correlates well with aurophilicity. This result also suggests that electronic perturbation caused by Au(I)-Au(I) interactions is important in explaining the reactivity of some dinuclear gold(I) complexes. The crystal structure for cis-dppee(Aul)2 shows short intramolecular Au(I)-Au(I) interactions of 2.9526 (6) A°, while the structure of trans-dppee(AuI)2 , shows intermolecular Au(I)-Au(I) interactions of 3.2292 (9) A°. The substitution of .As for P results in a ligand, cis-diphenylarsinoethylene (cis-dpaee), that is photochemically active, in contrast to the cis-dppee ligand. The complexes, cis-dpaee(AuX)2, are also photochemically active but with lower quantum yields than the cis-dppee(AuX)2 complexes.