Substitution derivatives of the heteronuclear cluster RuOs₃(μ-H)₂(CO)₁₃: Disubstituted group 15 derivatives

The structures in the solid state and solution state of tertiary group 15 ligand disubstituted derivatives of the heteronuclear cluster RuOs₃(μ-H)₂(CO)₁₃ are examined. Four structural types have been characterised crystallographically, including one in which both phosphine ligands were substituted at the unique ruthenium vertex. In solution, there are many more isomers present, most of which are rapidly interconverting via hydride migrations. Substitution appears to be directed electronically to the ruthenium vertex, although steric hindrance appears to drive subsequent isomerisation via migration of the second group 15 ligand.