Os(η 5 -B 5 H 10 ) 2 : A carbon-free analog of ferrocene

The synthesis of a carbon-free analog of ferrocene has been a long-standing goal in inorganic chemistry. We report here the preparation and crystallographic characterization of the carbon-free sandwich complex Os(η 5 -B 5 H 10 ) 2 , which is qualitatively similar to ferrocene in structure and bonding. The metal-ring bonding is much stronger in Os(η 5 -B 5 H 10 ) 2 , owing to rehybridization of the π molecular orbitals brought in by the bridging B-H-B hydrogens and the bent B-H t bonds of the larger B 5 H 10 ring (where B-H t is the terminal B-H bond). This also leads to an unusually short ring-ring separation of 3.071 angstroms and a staggered conformation. The isomeric Os(η 5 -B 5 H 10 )(η 3 -B 5 H 10 ), which features a coordination mode unknown for ferrocene, has also been isolated. A similar attempt for Ru(η 5 -B 5 H 10 ) 2 resulted only in Ru(η 5 -B 5 H 10 )(η 3 -B 5 H 10 ).