10.1021/ja064163k.s003
Wesley H. Bernskoetter
Wesley H.
Bernskoetter
Andrea V. Olmos
Andrea V.
Olmos
Jaime A. Pool
Jaime A.
Pool
Emil Lobkovsky
Emil
Lobkovsky
Paul J. Chirik
Paul J.
Chirik
N−C Bond Formation Promoted by a Hafnocene Dinitrogen Complex:
Comparison of Zirconium and Hafnium Congeners
American Chemical Society
2006
cycloaddition
hafnium imido character
equivalent
hafnocene dinitrogen
PhNCO
bond
2006-08-23 00:00:00
Dataset
https://acs.figshare.com/articles/dataset/N_C_Bond_Formation_Promoted_by_a_Hafnocene_Dinitrogen_Complex_Comparison_of_Zirconium_and_Hafnium_Congeners/3063580
Nitrogen−carbon bond formation from coordinated dinitrogen has been observed upon addition of 2 equiv of PhNCO to the hafnocene dinitrogen complex, [(η<sup>5</sup>-C<sub>5</sub>Me<sub>4</sub>H)<sub>2</sub>Hf]<sub>2</sub>(μ<sub>2</sub>,η<sup>2</sup>,η<sup>2</sup>-N<sub>2</sub>). 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, <i>p</i>-tolyl isocyanate, and <i>t</i>-BuC⋮CH 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 N<sub>2</sub> isomerization, as was observed with the zirconium congener.