A new mechanism for the conversion of transition metal azides to imido complexes.
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Density functional calculations reveal a new mechanism for the decomposition of rhenium alkyl azide. PhN3 binds to the rhenium center in an 1-diazoamino mode ([Re]N(Ph)NN) rather than the more common 1-terminal mode ([Re]N=N=NPh). From this new intermediate direct loss of N2 is fast, while the previously postulated cyclic 4-centered intermediate/transition state are very unfavorable in this system. Copyright 2008 American Chemical Society.
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