PSEUDO-ROTATIONAL INTERSYSTEM CROSSING IN D6 COMPLEXES

Intersystem crossings along the trigonal and rhombic twisting coordinates for a low-spin, six-coordinate, d6 complex (e.g., Fephen32+) are examined computationally. Molecular terms, including configuration interaction and spin-orbit coupling, are developed within the context of the angular overlap model. The Landau-Zener treatment of intersystem crossing yields a rate constant for racemization compatible with that of experiment and lends support to the interpretations of kinetic data that intersystem crossing is an integral part of the racemization process for Fephen32+. A brief examination of photoinduced racemization is given and implications for spin-equilibria complexes are discussed. © 1979, American Chemical Society. All rights reserved.