The electronic structure and photochemistry of transition metal thionitrosyl complexes

•The NS ligand is a weaker π acceptor than the NO ligand.•NS can be photoreleased from thionitrosyl complexes.•The reactivity of NS in solution is similar to NO.

A review of the electronic structure of transition metal thionitrosyl complexes is given. The optical spectra and EPR spectra of the complexes are discussed along with the results of theoretical calculations of the electronic structure including geometry optimizations. The σ donor and π donor/acceptor properties of the NS ligand are compared with the isovalent NO ligand. The photochemistry of thionitrosyl complexes is presented. The reactivity of the photoreleased NS radical in solution is discussed.

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