Abstract
This paper surveys thermal and photochemical reactivities of the cyanometallates. The thermal reactivity is described in connection with the unique properties of the cyanide ligand, whereas photochemical behaviour is discussed with reference to characteristics of the relevant excited states. For some hexacyano and pentacyanonitrosyl complexes the reactivity is interpreted using a simple INDO-type method. The modelling procedure for the thermal reactivity consists in interpreting the characteristics of the frontier orbitals, bond orders and charge distributions in the ground state, whereas photochemical reactivity is modelled by calculating the electronic structure of the selected excited states and analyzing the differences between the features of the ground and excited states.
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