Preferential formation of monogold(I) derivatives of [HRu 3W( η5-C 5H 5)(CO) 11BH] permits specificity in cluster linkage reactions: the crystal structure of [HRu 3W( η5-C 5H 5)(CO) 11B(AuPPh 3)

Abstract

Deprotonation of [HRu 3W( η 5-C 5H 5)(CO) 11BH] ( 1), occurs by loss of a proton bridging a B–H–Ru edge, and the remaining cluster-bound hydrogen atom in [HRu 3W( η 5-C 5H 5)(CO) 11B] − ( 2), is fluxional in solution. Anion 2 (isolated as the [(Ph 3P) 2N] + salt) reacts with [Ph 3PAuCl] to give [HRu 3W( η 5-C 5H 5)(CO) 11B(AuPPh 3)] ( 3) in high yield. The crystal structure of 3 illustrates that the gold(I) phosphine unit takes the place of the B–Ru bridging proton in 1. Reaction of [(Ph 3P) 2N][ 2] with [ClAu(dppf)AuCl] (dppf=1,1′-bis(diphenylphosphino)ferrocene) leads to [{HRu 3W( η 5-C 5H 5)(CO) 11BAu} 2(μ-dppf)] as the dominant product; [HRu 3W( η 5-C 5H 5)(CO) 11B(AuPPh 3)] is formed in low yield and apparently arises from phosphine exchange involving the [(Ph 3P) 2N] + cation.