Stabilization of high-valent metals by corroles: oxo[tris(pentafluorophenyl)corrolato]chromium(V).
The aerobic reaction of Cr(CO)6 with tris(pentafluorophenyl)corrole (H3(TpFPC)) in toluene gives the dark red oxochromium(V) compound (TpFPC)Cr(O), which has been characterized by X-ray crystallography, electrochemistry, and EPR spectroscopy. Short Cr-N (1.927-1.943 A) bonds as well as relatively large 14N and small 53Cr coupling constants suggest that sigma (N-->Cr) donation is responsible for the unusual stability of chromium(V) in this complex. The CrV/IV reduction potential (0.11 V vs Ag/AgCl) is 0.65 V below that of oxo(tetramesitylporphinato)chromium(V).
Meier-Callahan
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Beckman Institute, California Institute of Technology, Pasadena, California 91125, USA.
Gray
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Gross
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