PHOTOSUBSTITUTION AND PHOTOREDOX BEHAVIOR OF CYANOMETALATES - REACTION MODELS

This paper surveys thermal and photochemical reactivities of the cyano metallates. The thermal reactivity is described in connection with the unique properties of the cyanide ligand, whereas photochemical behavi our is discussed with reference to characteristics of the relevant exc ited states. For some hexacyano and pentacyanonitrosyl complexes the r eactivity is interpreted using a simple INDO-type method. The modellin g procedure for the thermal reactivity consists in interpreting the ch aracteristics of the frontier orbitals, bond orders and charge distrib utions in the ground state, whereas photochemical reactivity is modell ed by calculating the electronic structure of the selected excited sta tes and analyzing the differences between the features of the ground a nd excited states. (C) 1997 Elsevier Science S.A.