Synthesis and structure of cobalt(II) iodide bearing a bulky N-heterocyclic carbene ligand, and catalytic activation of bromoalkanes

A divalent cobalt iodine complex bearing 1,3-bis(mesityl) imidazol-2-ylidene and pyridine ligands was synthesized and its structure was determined. The cobalt center has a typical d(7)-tetrahedral geometry, as expected. Catalytic application of this cobalt complex with bromoalkanes and Grignard reagents demonstrated high-yield formation of alkenes as a result of beta-hydrogen elimination; in sharp contrast, the activation of alkyl halides was not successful using the larger N-heterocyclic carbene ligand, 1,3-bis(2,6-diisopropyl-phenyl)imidazol-2-ylidene. In the presence of styrene, Heck reaction proceeded with trans selectivity. The reaction of a substrate containing a bromobenzyl moiety yielded a homocoupling product. (C) 2012 Elsevier B.V. All rights reserved.