Gold(I) complexes of neutral, anionic, and oxidized bis (diphenylphosphino)acetonitrile

作者：Sithole Sicelo V; Staples Richard J; van Zyl Werner E^*

来源：Inorganic Chemistry Communications, 2012, 15: 216-220.

DOI：10.1016/j.inoche.2011.10.030

• Gold(I) complexes
• bis(diphenylphosphino)acetonitrile
• Pentafluorophenyl
• Dinuclear
• X-ray crystal structures

The ligand bis(diphenylphosphino)acetonitrile, (PPh2)(2)CHCN, (%26quot;dppm-CN%26quot;), was prepared. The reaction between dppm-CN and [Au(C6F5)(tht)] (tht = tetrahydrothiophene) (molar ratio 1:2) formed an open-ended dinuclear gold(I) complex [(AuC6F5)(2)(dppm-CN)], 1. The crystal structure showed a linear disposition of dimers with intramolecular Au center dot center dot center dot Au interactions between the dinuclear units, but despite two distinctly different distances between the gold centers, it is without intermolecular Au center dot center dot center dot Au interactions. Deprotonation of dppm-CN afforded the anion [(PPh2)(2)CCN](-) which reacted with [AuCl(tht)] (molar ratio 1:1) to form a neutral cyclic dinuclear gold(I) complex [Au-2{(PPh2)(2)CCN}(2)], 2. Complex 2 could also be formed from mono- or bis(phosphine) gold(l) chloride complexes through the making and breaking of Au-P bonds. Reaction between the oxidized, deprotonated form of the ligand, [(P(S)Ph-2)(2)CCN](-), and [AuCl(PPh3)] (molar ratio 1:1) formed the neutral mononuclear complex [Au(PPh3)(P(S)Ph-2)(2)CCN] 3, with the [AuPPh3](+) fragment bonded to one sulfur atom and a large degree of electron delocalization across the S-P-C-P-S ring. Complexes 1-3 were all obtained in satisfactory yield (70-90%), and analyzed by single crystal X-ray studies, solution 1H and P-31 NMR, IR, and elemental analyses.

• 出版日期2012-1