Gold(I) complexes containing ionic phosphine ligands with a cobaltocenium backbone

The reaction of (η⁵-R₂PC₅H₄)₂Co]PF₆] with (Me₂S)AuCl (1:2) resulted in {(η⁵-R₂PC₅H₄)₂Co](AuCl)₂}PF₆] (R = Ph, Cy, or ⁱ Pr). With a 1:1 ratio of (η⁵-R₂PC₅H₄)Co(η⁵-C₅H₅)]PF₆] to (Me₂S)AuCl, yellow crystalline {(η⁵-R₂PC₅H₄)Co(η⁵-C₅H₅)](AuCl)}PF₆] was produced. The reaction of {(η⁵-Cy₂PC₅H₄)Co(η⁵-C₅H₅)](AuCl)}PF₆] with phenyl acetylene gave {(η⁵-Cy₂PC₅H₄)Co(η⁵-C₅H₅)]Au(C≡C–Ph)]}PF₆], while the reaction of {(η⁵-Cy₂PC₅H₄)₂Co](AuCl)₂}PF₆] with phenyl acetylene produced the unusual ionic complex {(η⁵-Cy₂PC₅H₄)₂Co]Au(C≡C–Ph)]₂}Au(C≡C–Ph)₂]. The structure of this complex has been characterized by X-ray crystallography, and a possible pathway for its formation is suggested. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.