Preparation, structure and decomposition of gold(I) and gold(III) acetylide complexes

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• 作者：Schuster ; Oliver ; Liau ; Ruei-Yang ; Schier ; Annette ; Schmidbaur ; Hubert
• 关键词：Gold complexes ; Alkynylgold complexes ; Organogold complexes ; Alkynyl ligands ; Acetylide ligands ; Reductive elimination
• 刊名：Inorganica Chimica Acta
• 出版年：2005
• 出版时间：March 15, 2005
• 年：2005
• 卷：358
• 期：5
• 页码：1429-1441
• 全文大小：964 K

文摘

1-Alkynyl-dimethyl(triorganophosphine)gold(III) complexes of the type cis-Me₂(Ph₃P)AuaaaCCaaaR with R=H, Me, Ph (1aaa3) have been prepared from the cis-Me₂(Ph₃P)AuX (X=Cl, I) complexes and lithium alkynyls. The crystal structures of 1 and 2 have been determined together with those of the reference compounds cis-Me₂(Ph₃P)AuX (X=Cl, I) and cis-Me₂(Me₃P)AuI. The molecules have a standard square planar geometry and are not associated into oligomers. Due to the different hybridization of the carbon orbitals, the AuaaaC(CR) bonds are found significantly shorter than the AuaaaCH₃ bonds. Compounds 1aaa3 are stable colourless, crystalline solids at 20 aaC but decompose on heating with selective (cis) reductive elimination of ethane and formation of the gold(I) alkynyls (Ph₃P)AuaaaCCaaaR thus retaining the stronger gold-alkynyl bonds. Two complexes of this type have also been prepared by conventional routes from (R₃P)AuX complexes and the crystal structures of (Me₃P)AuaaaCCaaaPh and [(p-Tol)₃P]AuaaaCCaaaH have been determined. The former with the small Me₃P ligand is associated into two different trimers via aurophilic bonding and further aggregated into chains via weak inter-trimer contacts, while the latter is a monomer owing to the steric bulk of the (p-Tol)₃P ligand.