期刊
DALTON TRANSACTIONS
卷 41, 期 8, 页码 2213-2226出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c2dt10986g
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资金
- Department of Science and Technology [SR/S1/IC/0031/2010]
- Council of Scientific and Industrial Research, India [01/2358/09/EM-RII]
- CSIR, New Delhi
Recent advancement on the redox properties of a selection of transition metal complexes of the azoaromatic ligands: bidentate L-1 [2-(arylazo)pyridine] and tridentate HL2 [2-(aminoarylphenylazo)pyridine] are described and compared. Due to the presence of a low lying azo-centered pi*-orbital, these azoaromatic ligands may exist in multiple valent states. The coordination chemistry of the L-1 ligands was thoroughly studied during the 1980s. These complexes undergo facile reduction in solution at low accessible potentials. One electron reduced azo-complexes, though known for a long time to occur in solution, have only recently been isolated in a crystalline state. New synthetic protocols for the synthesis of metal-bound azo-radical complexes have been developed. Low-valent metal complexes such as metal carbonyls have been found to be excellent starting materials for this purpose. In a few selected cases, syntheses of these complexes were also achieved from very high valent metal oxides using triphenylphosphine as both a reducing and oxo-abstracting agent. Issues related to the ambiguities of the electronic structures in the azo-metal complexes have been discussed considering bond parameters, redox and spectral properties. Unusual redox events such as RIET (Redox-Induced Electron Transfer) phenomena in a few systems have been elaborated and compared with the known example. Novel examples of N=N bond cleavage reactions via four-electron reduction and subsequent C-N bond formation in metal-bound coordinated ligands have been noted.
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