Capturing In+ monomers in a neutral weakly coordinating environment

Titel Jurca; Justin Lummiss; Tara J Burchell; Serge I Gorelsky; Darrin S Richeson

doi:10.1021/ja901128q

Capturing In+ monomers in a neutral weakly coordinating environment

J Am Chem Soc. 2009 Apr 8;131(13):4608-9. doi: 10.1021/ja901128q.

Authors

Titel Jurca¹, Justin Lummiss, Tara J Burchell, Serge I Gorelsky, Darrin S Richeson

Affiliation

¹ Centre for Catalysis Research and Innovation and Department of Chemistry, University of Ottawa, Ottawa, Ontario, Canada K1N 6N5.

PMID: 19296581
DOI: 10.1021/ja901128q

Abstract

The application of a new bis(imino)pyridine ligand allowed the isolation and characterization of [{2,4-(t)Bu(2)C(6)H(3)N=CPh}(2)(NC(5)H(3))]In(+)(OTf)(-) as the first low-valent, main-group metal complex of this ligand scaffold. Structural analysis revealed a unique monomeric In(I) species with a surprisingly long metal-ligand bond. In conjunction with a density functional theory investigation, this complex is shown to display only nominal donor-acceptor interactions between the metal and the neutral ligand. The mixing of the occupied 5s metal orbital with the occupied ligand orbitals reduces the reactivity of the central atom and thus stabilizes this species. An In(III) species, [{2,4-(t)Bu(2)C(6)H(3)N=CPh}(2)(NC(5)H(3))]InCl(2)(+)InCl(4)(-) was also isolated and structurally characterized utilizing this ligand frame.