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A Carbon-Free Sandwich Complex [(P5)2Ti]2−

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Science  01 Feb 2002:
Vol. 295, Issue 5556, pp. 832-834
DOI: 10.1126/science.1067325

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Abstract

Reactions of highly reduced titanium complexes with white phosphorus, P4, at or below 25°C yielded brown to deep red-brown salts of the first entirely inorganic metallocene, [(η5-P5)2Ti]2−(1). Like ferrocene and other carbon-based metallocenes, the structure of1 has parallel and planar five-membered rings symmetrically positioned about the central metal atom. Despite its electron-deficient (16 electron) and formally zerovalent titanium character, salts of1 are highly stable toward heat and air, both in solution and in the solid state. Computational studies show that the pentaphosphacyclopentadienyl unit, P5, functions as an unusually effective acceptor ligand, and this results in substantial stabilization of 1.

  • * Present address: Department of Chemistry, Michigan Technological University, Houghton, MI 49931, USA.

  • To whom correspondence should be addressed. E-mail: urnezius{at}mtu.edu, ellis{at}chem.umn.edu

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