title: N2 hydrogenation from activated end-on bis(indenyl) zirconium dinitrogen complexes.
abstract: Sodium amalgam reduction of the bis(indenyl)zirconium dihalide complexes, (eta5-C9H5-1-iPr-3-Me)2ZrX2 (X = Cl, Br, I), yielded the corresponding end-on dinitrogen complexes, [(eta5-C9H5-1-iPr-3-Me)2Zr(NaX)]2(mu2, eta1, eta1-N2), with inclusion of 1 equiv of salt per zirconocene. The solid state structures of the chloro and iodo congeners establish short Zr N and elongated N N bonds, consistent with modest to strong activation of the coordinated dinitrogen molecule. Exposure of the N2 compounds to 1 atm of dihydrogen resulted in rapid N H bond formation to yield a hydrido zirconocene hydrazido compound concomitant with salt elimination. These studies establish a new structural type of zirconocene dinitrogen complex and demonstrate that side-on coordination of the N2 ligand in the ground state is not a prerequisite for dinitrogen hydrogenation.
authors.affiliation: Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York 14853, USA.
authors.forename: Doris
authors.initials: D
authors.lastname: Pun
authors.forename: Christopher A
authors.initials: CA
authors.lastname: Bradley
authors.forename: Emil
authors.initials: E
authors.lastname: Lobkovsky
authors.forename: Ivan
authors.initials: I
authors.lastname: Keresztes
authors.forename: Paul J
authors.initials: PJ
authors.lastname: Chirik