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Tertiary group 15 ligand monosubstituted derivatives of the heteronuclear cluster RuOs 3 (l-H) 2 (CO) 13 have been prepared and their solid state and solution structures examined. A number of isomeric structural types have been identified in solution, and these appear to be correlated to disorder in the solid state. Hydride fluxionality and restricted rotation about the metal-phosphorus bond have also been observed.