N−C Bond Formation Promoted by a Hafnocene Dinitrogen Complex:  Comparison of Zirconium and Hafnium Congeners

Wesley H. Bernskoetter, Andrea V. Olmos, Jaime A. Pool, Emil Lobkovsky, and Paul J. Chirik*
Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York 14853
J. Am. Chem. Soc., 2006, 128 (33), pp 10696–10697
DOI: 10.1021/ja064163k
Publication Date (Web): July 29, 2006
Copyright © 2006 American Chemical Society
*

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

, pc92@cornell.edu

Abstract

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Nitrogen−carbon bond formation from coordinated dinitrogen has been observed upon addition of 2 equiv of PhNCO to the hafnocene dinitrogen complex, [(η5-C5Me4H)2Hf]2(μ2,η2,η2-N2). The resulting product most likely arises from initial NC cycloaddition of the first equivalent of heterocumulene, followed by carbonyl insertion of a second equivalent into the newly formed hafnium−nitrogen bond. The resulting product has considerable hafnium imido character, as evidenced by the metrical parameters determined from the solid-state structure as well as reactivity studies, whereby PhNCO, p-tolyl isocyanate, and t-BuCCH each undergo cycloaddition with the hafnium−nitrogen bond. The origin of the nitrogen−carbon-forming chemistry is likely derived from the reluctance of the hafnocene dinitrogen complex to undergo ligand-induced N2 isomerization, as was observed with the zirconium congener.

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History

  • Published In Issue August 23, 2006
  • Received June 13, 2006

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