Preparation and Oxygenation of Cobalt N‐Confused Porphyrin Nitrosyl Complexes

Abstract

Abstract The nitrosylation of Co( H CTPP) ( 1 ) in CH 2 Cl 2 afforded [Co(CTPP C 2 H 2 Cl )(NO)] ( 2 ) with a chlorovinyl group substituent on the inner carbon atom of the N‐confused porphyrin ring. The spectroscopic data suggest that 1 exhibits an {Co(NO)} 8 electronic structure. The nitrosylation of 1 in the presence of oxygen leads to [Co(CTPP O )(NO)] ( 3 ), which is a {Co(NO)} 7 cobalt nitrosyl complex. A bent axial Co–N–O conformation was observed in both nitric oxide complexes with an angle of 128.5(7)° for 2 and 146.9(11)° for 3 . An sp 3 hydride carbon atom was evidenced in the crystal structure of 2 , and an η 2 interaction between the cobalt center and the inner carbonyl group was observed. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)