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Synthesis and Coordination Chemistry of Gold(I) Acetylides. The Solid-State Structure of {[η2-(Ph3P)AuC⋮CFc]Cu(μ-Cl)}2

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journal contribution
posted on 20.04.2001, 00:00 by Heinrich Lang, Stefan Köcher, Stephan Back, Gerd Rheinwald, Gerard van Koten
The gold(I) acetylide (Ph3P)AuC⋮CC6H3(CH2NMe2)2-3,5 (3) is accessible by the reaction of (Ph3P)AuCl (1) with HC⋮CC6H3(CH2NMe2)2-3,5 (2) in a 1:1 molar ratio. Base-catalyzed desilylation of (Ph3P)AuC⋮CSiMe3 (4) produces the homobimetallic gold(I) species (Ph3P)AuC⋮CAu(PPh3) (5). However, the intermediate formation of (Ph3P)AuC⋮CH could not be evidenced, but is most likely. The coordination chemistry of 5 and (Ph3P)AuC⋮CFc (6) toward different copper(I) halides [CuX]n (7a, X = Cl; 7b, X = Br) is presented. While heterodinuclear 6 affords with equimolar amounts of 7a hexanuclear {[η2-(Ph3P)AuC⋮CFc]Cu(μ-Cl)}2 (8), homobinuclear 5 produces with 7b in a 1:1 molar ratio via ligand exchange polymeric [CuC⋮C]n (10) and mononuclear (Ph3P)AuBr (11). A feasible reaction mechanism for the formation of the latter species is presented. The solid-state structure of 8 is reported. It exhibits a linear array around the gold(I) center and a coplanar arrangement of the Cu2Cl2 and the gold(I) acetylide entities.