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DOI: 10.1039/A900808J (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1999, 2077-2086

Synthesis, structural characterization and reactivities of hexaosmium carbonyl clusters with six-membered cyclic thioether and thioxane ligands

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Kelvin Sze-Yin Leung and Wing-Tak Wong

Abstract

Cluster complexes [Os6(CO)15{[upper bond 1 start]S(CH2)4C[upper bond 1 end]H2}{µ-[upper bond 1 start]S(CH2)4C[upper bond 1 end]H2}] 1 and [Os5(CO)15{[upper bond 1 start]S(CH2)4C[upper bond 1 end]H2}] 2 were isolated from the reaction of [Os6(CO)16(MeCN)2] with [upper bond 1 start]S(CH2)4C[upper bond 1 end]H2 (L1) in 24 and 22% yields respectively. Cluster degradation from 1 to 2 can be achieved by addition of a stoichiometric quantity of L1 in CHCl3 under reflux. Monosubstituted cluster complex [Os6(CO)16{µ-[upper bond 1 start]S(CH2)3SC[upper bond 1 end]H2}] 3 containing a [upper bond 1 start]S(CH2)3SC[upper bond 1 end]H2 (L2) ligand bridging across an Os–Os edge via one of the sulfur atoms was isolated in good yield from a similar reaction. However, similar reaction between [Os6(CO)16(MeCN)2] and [upper bond 1 start]S(CH2)2SCH2C[upper bond 1 end]H2 (L3) gave [Os6(CO)16{[upper bond 1 start]S(CH2)2SCH2C[upper bond 1 end]H2}2] 4 as the major product instead. The two thio ligands are found to co-ordinate in terminal fashion to two different vertices of the Os6 core. Interaction of tridentate sulfur donor ligand [upper bond 1 start]SCH2SCH2SC[upper bond 1 end]H2 (L4) with [Os6(CO)16(MeCN)2] afforded [Os6(CO)14(µ-CO)([upper bond 1 start]SCH2SCH2SC[upper bond 1 end]H2)] 5 in which the ligand L4 was found to cap over a triangular face of the Os6 skeleton. Treatment of mixed-donor ligand [upper bond 1 start]S(CH2)2OCH2C[upper bond 1 end]H2 (L5) yielded a pair of isomeric complexes [Os6(CO)15{[upper bond 1 start]S(CH2)2OCH2C[upper bond 1 end]H2}{µ-[upper bond 1 start]S(CH2)2OCH2C[upper bond 1 end]H2}] 6 and [Os6(CO)15{[upper bond 1 start]O(CH2)2SCH2C[upper bond 1 end]H2}{µ-[upper bond 1 start]S(CH2)2OCH2C[upper bond 1 end]H2}] 7. Carboxylation of 6 gave [Os6(CO)16{µ-[upper bond 1 start]S(CH2)2OCH2C[upper bond 1 end]H2}] 8 and [Os6(CO)18]. Hydrogenation of 6 led to the formation of dihydrido cluster [Os6(CO)15(µ-H)2{[upper bond 1 start]S(CH2)2OCH2C[upper bond 1 end]H2}{µ-[upper bond 1 start]S(CH2)2OCH2C[upper bond 1 end]H2}] 9. The metal skeleton of 9 can be described as two fused tetrahedra sharing a common edge. All new compounds were fully characterized by spectroscopic and analytical techniques. In addition the structures of 1, 2, 3, 4, 5, 6, 8 and 9 were established by X-ray crystallography.

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