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Isolation, X-ray single crystal and theoretical study of quinquevalent metal oxoisopropoxides, Nb6O8(iPrO)14(iPrOH)2 and Re4O6(OiPr)10статья
- Авторы: Seisenbaeva Gulaim A., Baranov Alexei I., Shcheglov Pavel A., Kessler Vadim G.
- Журнал: Inorganica Chimica Acta
- Том: 357
- Номер: 2
- Год издания: 2004
- Издательство: Elsevier BV
- Местоположение издательства: Netherlands
- Первая страница: 468
- Последняя страница: 474
- DOI: 10.1016/s0020-1693(03)00499-7
- Аннотация: Oxoisopropoxide complexes of niobium, Nb6O8(iPrO)14(iPrOH)2 (I), and rhenium, Re4O6(OiPr)10 (II), were isolated as byproducts of anodic oxidation of these metals in iPrOH in the presence of LiCl as conductive additive. The common feature of both structures consists in the occurrence in their molecules of an M4O16 planar core formed in the formal absence of M–M bonding for I and in the presence of electron-deficient but surprisingly short (Re–Re 2.52–2.54 Å) metal–metal bonds in II. The stability of this core for the oxoalkoxide derivatives of rhenium(V,VI) and niobium(V) and poor stability for those of tantalum(V) are discussed based on the results of quantum-chemical calculations. New oxoisopropoxide complexes of Nb(V) and Re(V,VI) were isolated as byproducts of anodic oxidation of these metals in iPrOH. Both structures contain an M4O16 planar core. The stability of this core for the alkoxide complexes appears to be due to its specific stabilization via M–O π-bonding, which find its confirmation in the calculation results presented in this work.
- Добавил в систему: Щеглов Павел Александрович