Synthesis and Structure of a Zirconium Dinitrogen Complex with a Side-On Bridging N(2) Unit

Jonathan D. Cohen; Michael D. Fryzuk; Thomas M. Loehr; Murugesapillai Mylvaganam; Steven J. Rettig

doi:10.1021/ic9709786

Synthesis and Structure of a Zirconium Dinitrogen Complex with a Side-On Bridging N(2) Unit

Inorg Chem. 1998 Jan 12;37(1):112-119. doi: 10.1021/ic9709786.

Authors

Jonathan D. Cohen¹, Michael D. Fryzuk, Thomas M. Loehr, Murugesapillai Mylvaganam, Steven J. Rettig

Affiliation

¹ Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, BC, Canada V6T 1Z1, and Department of Biochemistry and Molecular Biology, Oregon Graduate Institute of Science and Technology, Portland, Oregon 97291-1000.

PMID: 11670268
DOI: 10.1021/ic9709786

Abstract

Reduction of Zr(O-2,6-Me(2)C(6)H(3))Cl(2)[N(SiMe(2)CH(2)PPr(i)(2))(2)] with sodium amalgam under dinitrogen yields the dinuclear zirconium dinitrogen complex {[(Pr(i)(2)PCH(2)SiMe(2))(2)N]Zr(O-2,6-Me(2)C(6)H(3))}(2)(&mgr;-eta(2):eta(2)-N(2)). Solid state structural analysis shows that the dinitrogen unit is bound in a side-on mode of coordination with the N-N bond distance at 1.528(7) Å; resonance Raman spectra show a band at 751 cm(-)(1) for nu(N-N), which is consistent with this very long bond. In addition, the N(2) ligand is hinged slightly so that the Zr(2)(&mgr;-eta(2):eta(2)-N(2)) core adopts a flattened butterfly shape rather than a completely planar core as found in other related systems. Other Zr(IV) precursors of the general formula ZrCl(2)X[N(SiMe(2)CH(2)PPr(i)(2))(2)] (X = OBu(t), OCHPh(2), NPh(2)) either decompose upon reduction under N(2) or produce mixtures of products.