期刊
COORDINATION CHEMISTRY REVIEWS
卷 250, 期 17-18, 页码 2325-2334出版社
ELSEVIER SCIENCE SA
DOI: 10.1016/j.ccr.2006.03.004
关键词
photochemistry; azide complexes; redox processes; azidyl radical; nitrene formation; nitrido ligand
Results obtained to date document that inorganic compounds containing azide-moiety undergo several kinds of photochemical processes, the most extensively studied being (i) singlet or triplet six-electron nitrene (-N) intermediate formation at a dinitrogen molecule elimination from the azido ligand preserving the central atom oxidation state; (ii) transformation of azido (-N-3) to nitrido (equivalent to N) complexes associated with a two-electron oxidation of the central atom; (iii) oxidation of azido anionic ligand (N-3(-)) to its radical (N-3(center dot)) accompanied by a one-electron reduction of the central atom; (iv) non-redox photoejection of azido ligands from the coordination sphere or its substitution, usually for a solvent molecule; (v) photoisomerization reaction; (vi) reaction of other than azido ligand in the primary coordination sphere; (vii) reactions of azido group being peripheral part of organic ligands. Moreover, azido complexes are involved in pure photophysical deactivation processes without any chemical change. This contribution is aimed at reviewing all of the mentioned deactivations. (c) 2006 Elsevier B.V. All rights reserved.
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