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Selected Works of Michael P. Castellani
Article
Synthesis, Characterization, and Crystal Structure of the (η5-C5Ph5)Cr(CO)3 Radical
Chemistry Faculty Research
  • Ray J. Hoobler
  • Marc A. Hutton
  • Mills M. Dillard
  • Michael Castellani, Marshall University
  • Arnold L. Rheingold
  • Anne L. Rieger
  • Philip H. Rieger
  • Thomas C. Richards
  • William E. Geiger
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Document Type
Article
Publication Date
1-1-1993
Disciplines
Abstract

The reaction between Cr(CO)6 and Na(C5Ph5 ) in refluxing diglyme yields [Na(diglyme)3/2][(C5Ph5)Cr(CO)3], 1. Metathesis of 1 with [Ph3P=N=PPh3 ]Cl in CH2Cl2 yields [Ph3P=N=PPh3][(C5Ph5)Cr(CO)3], 2. Oxidation of 1 by AgBF4 in cold THF under an argon atmosphere produces (C5Ph5)Cr(CO)3, 3. Complexes 2 and 3 form a redox pair connected by a quasireversible one-electron process, E0 = -0.69 V vs ferrocene in CH2Cl2, E0 = -0.50 V in CH3CN, ks = 0.12 cm/s. ESR spectra of (C5Ph5)Cr(CO)3 in toluene at 90 K gave a rhombic g-tensor with components 2.1366, 2.0224, and 1.9953, consistent with the expected low-spin d5 electronic configuration. The largest g-tensor component was significantly temperature dependent, suggesting an equilibrium between conformations with 2A´ and 2A˝ ground states. Crystal structures of [Ph3P=N=PPh3][(C5Ph5)Cr(CO)3] and (C5Ph5)Cr(CO)3 were obtained.

Comments

This is the authors’ peer-reviewed manuscript. The version of record is available from the publisher at http://dx.doi.org/10.1021/om00025a023. Copyright ©1992 American Chemical Society. All rights reserved.

Citation Information
Hoobler, R. J.; Hutton, M. A.; Dillard, M. M.; Castellani, M. P.; Rheingold, A. L.; Rieger, A. L.; Rieger, P. H.; Richards, T. C.; Geiger, W. E., Synthesis, characterization, and crystal structure of the (η5-C5Ph5) Cr (CO) 3 radical. Organometallics. 1993;12(1):116-23.