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Dihydrogen Complexes of Electrophilic Metal Centers: Observation of Cr(CO)₅(H₂), W(CO)₅(H₂) and [Re(CO)₅(H₂)]⁺

Steven L. Matthews, Vincent Pons, and D. Michael Heinekey*

Department of Chemistry, University of Washington, Box 351700, Seattle, Washington 98195-1700

J. Am. Chem. Soc., 2005, 127 (3), pp 850–851

DOI: 10.1021/ja0433370

Publication Date (Web): December 24, 2004

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

, heinekey@chem.washington.edu

Abstract

Photolysis of dichloromethane solutions of M(CO)₆ (M = Cr, W) at low temperature in the presence of hydrogen gas affords W(CO)₅(H₂) (1) and Cr(CO)₅(H₂) (2). Complexes 1 and 2 are characterized as dihydrogen complexes based on short T₁ values for the hydride resonances and a large HD coupling of 35.3 Hz (W) and 35.8 Hz (Cr) in the HD derivatives. A cationic analogue, [Re(CO)₅(H₂)]⁺ (3), was prepared by reaction of Re(CO)₅Cl with [Et₃Si][B(C₆F₅)₄] in fluorobenzene under hydrogen. Complex 3-d₁ exhibits J_HD = 33.9 Hz. Complex 3 is strongly acidic, with complete deprotonation by diethyl ether; complexes 1 and 2 are moderately acidic. Deprotonation of 1 is complete in the presence of one equivalent of triethylamine.

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Published In Issue January 26, 2005
Received November 4, 2004

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Communication

Dihydrogen Complexes of Electrophilic Metal Centers: Observation of Cr(CO)₅(H₂), W(CO)₅(H₂) and [Re(CO)₅(H₂)]⁺