Journal
CHEMICAL COMMUNICATIONS
Volume 48, Issue 5, Pages 635-653Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c1cc14592d
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- Ministero dell'Istruzione, dell'Universita e della Ricerca (MIUR, Roma)
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The chemistry of niobium and tantalum pentahalides, MX5, with oxygen compounds is reviewed herein. The polynuclear structure of MX5 is readily broken by addition of oxygen-containing organic molecules, L, to give either mononuclear or ionic dinuclear coordination adducts. Then activation of the organic ligand may take place favoured by several factors, i.e. low M-X bond energy, high temperature, presence of more than one oxygen function within L, L/M molar ratio >= 2. The activation reactions are often uncommon in the context of metal halides; they include the cleavage of C-sp3-O, C-sp2-O, C-H and C-C bonds, and eventual successive rearrangements proceeding with C-O or C-C couplings. The recently elucidated reactivity of MX5 with limited amounts of oxygen compounds will be presented, and possible connections with the relevant MX5-directed syntheses reported in the literature will be outlined.
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