Homoleptic tetranuclear osmium carbonyls: from the rhombus via the butterfly to the tetrahedron

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The structures of the tetranuclear osmium carbonyl derivatives Os4(CO)n (n = 16, 15, 14, 13, 12) have been investigated using the density functional theory method MPW1PW91 with the SDD effective core potential basis set, found to be effective in previous work for the study of Os3(CO)12. The Os4 clusters in the lowest energy structures for Os4(CO)16, Os4(CO)15, and Os4(CO)14 are found to be rhombi, butterflies, and tetrahedra with four, five, and six Os-Os bonds, respectively, in accord with structures determined by X-ray diffraction as well as the 18-electron rule. The fluxionality of tetrahedral Os4(CO)14, suggested by experimental work of Johnston, Einstein, and Pomeroy, is confirmed by our DFT studies, which find four Os4(CO)14 structures within 1.5 kcal mol-1 of each other with similar tetrahedral Os4 frameworks but with different arrangements of bridging and semibridging carbonyl groups. The lowest energy structures for the more unsaturated Os4(CO)13 and Os4(CO)12 are also based on Os4 tetrahedra but with shorter Os-Os edge lengths than in Os4(CO)14 suggesting delocalized multiple bonding in the more highly unsaturated systems. Thus the global minimum for Os4(CO)12 is predicted to have tetrahedral symmetry, with all terminal carbonyl groups analogous to the experimentally known structure of (mu3-H)4Re3(CO)12, but without the face-bridging hydrogen atoms.