Coordination chemistry of dimethylgold halides with bidentate phosphorus and arsenic ligands - revisited

Article abstract of DOI:10.1002/cber.19961290116

Dimethylgold(III) chloride and bromide, (Me₂AuX)₂, react with bisfdiphenylphosphanyljmethane (dppm, molar ratio 1:2) to give the P-rnonohapto complexes cis-Me₂AuX(dppm) (1a, to) in quantitative yields. The products are readily oxidized by air to yield the P-hapto P'-monoxides 2a, b. Treatment of 1a, b with AgNO₃ affords an ionic nitrate [Me₂Au(dppm)]₂ [NO₃^-] ₂ (1c), which contains a dinuclear cation. A mixed bromide/nitrate (from 1b and half the equivalent amount of AgNO₃) is thermally unstable and undergoes elimination of ethane to give an ionic tetranuclear gold (I) complex [(dppm)₄Au₄Br₂]² [NO₃^-]₂ (3b). - Treatment of (Me₂AuCl)₂ with CH₂(AsPh₂)₂ (dpam, molar ratio 1:2) gives cJs-Me₂-AuCl(dpam) (1d), the arsenic analog of 1a, which is not sensitive to oxygen. -The reaction of bis(diphenylphosphanyl)amine (dppa) yields 1:1 P-monohapto adducts Me₂AuX(dppa), which are in equilibrium with ionic chelated systems Me₂Au(dppa)⁺ X^- (1e, f). Complex 1e is readily oxidized by air to the P-hapto P′-monoxide cis complex 2e. Treatment of le with AgNO₃ gives the ionic nitrate Me₂. Au(dppa)⁺ NO₃^- (1g). - All compounds were identified by standard analytical and spectroscopic techniques. The crystal structures of 2a, 3b, 1d, and 2e were determined by single-crystal X-ray diffraction studies. VCH Verlagsgesellschaft mbH, 1996.