The mechanism of insertion of an acetylene into the methylgold bond: structure of a reaction intermediate

Abstract

The determination of the structure of a reaction intermediate gives strong evidence for an unusual mechanism of insertion of an acetylene into the methylgold bond.

Theoretical study of the d10–d8 interaction between Au(I) and Au(III) on the cis/trans-[PH3Au(I)C(L)C(L)Au(III)(R)2PH3] (R=–H, –CH3; L=–H, –CH3) systems

“…In particular, the system of our interest that shows d 8 [17]. The experimental distance between Au(I) and Au(III) centers has been reported to be 331 pm in the cis-isomer, pointing to an intramolecular interaction.…”

Fundamental Elementary Steps in Gold Chemistry

“…Puddephatt et al [111,112] reported early on the reaction of Me 3 PAuMe with hexafluorobutyne to give rapidly a mixed-oxidation state dinuclear Au(I)/Au(III) complex that was structurally characterized (Scheme 3.40). The Au(III) fragment of this species undergoes slowly reductive elimination and provides, depending on the solvent, either the formal product of a syn insertion reaction of the alkyne into the Au-Me bond (pathway a)) or ethane and a corresponding Au(I)/Au(I) dinuclear complex (pathway b)).…”

Superconductivity in Copper, Silver, and Gold Compounds

“…CuO : CuO has a tenorite structure in which each Cu II is surrounded by four coplanar bonds 51. 52 However, no layered plane structure is formed as is the case in La 2 CuO 4 and YBa 2 Cu 3 O 7 . The half empty 3d orbital is in the local plane, but corresponding orbitals on different sites are not in the same plane.…”