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Structure and Reactivity of a Hafnocene μ-Nitrido Prepared From Dinitrogen Cleavage


  • We thank the Director of the Office of Basic Energy Science Chemical Sciences Division, U.S. Department of Energy (DE-FG-02-05ER15659) and the ACS Frasch Foundation for financial support. S.P.S. thanks the Natural Sciences and Engineering Research Council of Canada for a predoctoral fellowship and C.M. also acknowledges the Alexander von Humboldt Foundation for a Feodor Lynen postdoctoral fellowship.


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Carbonylation of the strongly activated hafnocene dinitrogen complex, [{(η5-C5H2-1,2,4-Me3)2Hf}2222-N2)], in the presence of electron-rich 4-substituted pyridines resulted in isolation of rare μ-nitrido hafnocene complexes prepared from N2 cleavage. The electronic and molecular structures as well as the intermediacy in N[BOND]C bond forming reactions has been determined.