title: Unusual κ1 coordination of a β-diketiminate ligand in niobium complexes.
abstract: Reaction of (BDI)Nb(N(t)Bu)Cl2py with NaCp results in the κ(1)-coordination of the BDI ligand in the complex (κ(1)-N,BDI)CpNb(N(t)Bu)Cl (2). Via chloride abstraction from 2, we develop synthetic routes to structurally analogous cationic and Nb(IV) pseudo-four coordinate complexes where the BDI ligand returns to the κ(2)-coordination mode. We compare these to our previously reported tetrahedral niobium bis(imido) complexes to investigate the effects of the Cp ligand on the properties of Nb-BDI-imido systems. Substitution of the chloride in 2 with a hydride also causes return to bidentate binding of the BDI ligand. The X-ray crystal structures of these complexes have been determined, and the structural parameters reflecting the consequences of the electronic differences are discussed.
authors.affiliation: Department of Chemistry, University of California, Berkeley, California 94720, USA. arnold@berkeley.edu rbergman@berkeley.edu.
authors.forename: Jessica A
authors.initials: JA
authors.lastname: Ziegler
authors.affiliation: Department of Chemistry, University of California, Berkeley, California 94720, USA. arnold@berkeley.edu rbergman@berkeley.edu.
authors.forename: Robert G
authors.initials: RG
authors.lastname: Bergman
authors.affiliation: Department of Chemistry, University of California, Berkeley, California 94720, USA. arnold@berkeley.edu rbergman@berkeley.edu.
authors.forename: John
authors.initials: J
authors.lastname: Arnold