Sodium amalgam reduction of the bis(indenyl)zirconium dihalide complexes, (η5-C9H5-1-iPr-3-Me)2ZrX2 (X = Cl, Br, I), yielded the corresponding end-on dinitrogen complexes, [(η5-C9H5-1-iPr-3-Me)2Zr(NaX)]2(μ2, η1, η1-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 dihydrogenresulted 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.
All Science Journal Classification (ASJC) codes
- Colloid and Surface Chemistry