The reaction of the octahedral borido cluster [Rh 2 Ru 4 (CO) 1 6 B] - (which exists as trans and cis isomers with respect to the Rh sites) with [ClAu(dppb)AuCl] (dppb=bis(diphenylphosphino)butane) leads to the formation of separable isomers [{cis-Rh 2 Ru 4 (CO) 1 6 B} 2 {μ-Au(dppb)Au}] and [{trans-Rh 2 Ru 4 (CO) 1 6 B} 2 {μ-Au(dppb)Au}]. The cis-isomer converts rapidly to the trans-isomer. A similar reaction with [ClAu(dppm)AuCl] (dppm=bis(diphenylphosphino)methane) gives the linked dicluster [{Rh 2 Ru 4 (CO) 1 6 B} 2 {μ-Au(dppm)Au}], accompanied by the formation of [Rh 2 Ru 4 (CO) 1 5 BAu(dppm)] and [RhRu 4 (CO) 1 4 BAu 2 (dppm)], as well as the unstable [Rh 2 Ru 4 (CO) 1 6 B{Au(dppm)AuCl}]. The crystal structures of [{trans-Rh 2 Ru 4 (CO) 1 6 B} 2 {μ-Au(dppb)Au}] and [RhRu 4 (CO) 1 4 B{Au(dppm)Au}] have been determined; the former retains octahedral borido Rh 2 Ru 4 B units, while the latter is the consequence of cluster degradation and contains a square-based pyramidal RhRu 4 B unit capped on the square-face by the two gold atoms (Au-Au=2.878(1) 9) of a {Au(dppm)Au} unit.