Substitution Reactions of (C5Ph5)Cr(CO)3: Structural, Electrochemical, and Spectroscopic Characterization of (C5Ph5)Cr(CO)2L, L = PMe3, PMe2Ph, P(OMe)3

Authors

D. John Hammack
Mills M. Dillard
Michael Castellani, Marshall UniversityFollow
Arnold L. Rheingold
Anne L. Rieger
Philip H. Rieger

Document Type

Article

Publication Date

1996

Abstract

The radical complex (C₅Ph₅)Cr(CO)₃ reacts with small, neutral, monodentate Lewis bases (PMe₃, PMe₂Ph, P(OMe)₃) in THF at −78 °C (PMe₂Ph reacts at ambient temperature) to yield the monomeric substitution products (C₅Ph₅)Cr(CO)₂L·THF as thermally stable solids. Electrochemical and spectroscopic data are provided. An X-ray crystal structure of the hemisolvate (C₅Ph₅)Cr(CO)₂PMe₃·0.5THF was obtained. Frozen-solution ESR spectra of (C₅Ph₅)Cr(CO)₂L in toluene are comparable to those of other low-spin d⁵ “piano-stool” complexes. Rotation of the Cr(CO)₂L moiety relative to the C₅Ph₅ ring is rapid on the ESR time scale in low-temperature liquid solutions and leads to axial powderlike spectra. Analysis of this effect leads to significant insights into the electronic structure.

Comments

This is the authors’ peer-reviewed manuscript. The version of record is available from the publisher at http://dx.doi.org/10.1021/om960374u. Copyright © 2018 American Chemical Society. All rights reserved.

Recommended Citation

Hammack, D. J.; Dillard, M. M.; Castellani, M. P.; Rheingold, A. L.; Rieger, A. L.; Rieger, P. H., Substitution Reactions of (C5Ph5)Cr (CO)3: Structural, Electrochemical, and Spectroscopic Characterization of (C5Ph5)Cr(CO)2L (L= PMe3, PMe2Ph, P (OMe)3). Organometallics 1996, 15 (22), 4791-4797.