Preferential formation of monogold(I) derivatives of [HRu3W(eta(5)-C5H5)(CO)(11)BH] permits specificity in cluster linkage reactions: the crystal structure of [HRu3W(eta(5)-C5H5)(CO)(11)B(AuPPh3)]

Deprotonation of [HRu3W( eta(5)-C5H5)(CO)(11)BH] (1), occurs by loss of a p roton bridging a B-H-Ru edge, and the remaining cluster-bound hydrogen atom in [HRu3W(eta(5)-C5H5)(CO)(11)B](-) (2), is fluxional in solution. Anion 2 (isolated as the [(Ph3P)(2)N](+) salt) reacts with [Ph3PAuCl] to give [HRu 3W(eta(5)-C5H5)(CO)(11)B(AuPPh3)] (3) in high yield. The crystal structure of 3 illustrates that the gold(I) phosphine unit takes the place of the B-R u bridging proton in 1. Reaction of [(Ph3P)(2)N][2] with [ClAu(dppf)AuCl] ( dppf=1,1'-bis(diphenylphosphino)ferrocene) leads to [{HRu3W(eta(5)-C5H5)(CO )(11)BAu}(2)(mu-dppF)] as the dominant product; [HRu3W(eta(5)C(5)H(5))(CO)( 11)B(AuPPh3)] is formed in low yield and apparently arises from phosphine e xchange involving the [(Ph3P)(2)N](+) cation. (C) 1999 Elsevier Science Ltd . All rights reserved.