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Published December 17, 2001 | Supplemental Material
Journal Article Open

Chromium Corroles in Four Oxidation States

Abstract

We have isolated and characterized chromium complexes of 5,10,15-tris(pentafluorophenyl)corrole [(tpfc)H_3] (1) in four oxidation states:  [(tpfc•)CrO][SbCl_6] (6); [(tpfc)CrO] (2); [(tpfc)CrO][Cp_2Co] (4); and [(tpfc)Cr(py)_2] (3). Complex 6 was prepared both by electrochemical and chemical oxidation of 2; its formulation as a Cr^VO ligand−radical species is based on UV−visible absorption as well as EPR measurements. Cobaltocene reduction of 2 gave 4; it was identified as a diamagnetic d^2 Cr^(IV)O complex from its sharp ^1H NMR spectrum. Reaction of 2 with triphenylphosphine yielded a chromium(III) corrole, [(tpfc)Cr(OPPh_3)_2] (5). Owing to its air sensitivity, 5 could not be isolated in the absence of excess OPPh_3. The structure of the Cr^(III) bis-pyridine complex (3) was determined by X-ray crystallography (Cr−N distances:  1.926−1.952 Å, pyrrole; 2.109, 2.129 Å, pyridine).

Additional Information

© 2001 American Chemical Society. Received 9 July 2001. Published online 20 November 2001. Published in print 1 December 2001. This work was supported by the NSF (H.B.G.), the Bayer Corporation, and the Israel Science Foundation (Z.G.).

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