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Mono- and Dinuclear Heteroleptic Cobalt Complexes with α-Diimine and Polyarene Ligands
Xuting Wang1, Yanxia Zhao1, Shida Gong2
1Key Laboratory of Synthetic and Natural Functional Molecular, Chemistry of the Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi'an 710069 (P.R. China).
Abstract:
Reactions of the dimeric cobalt complex [(L(-) Co)2 ] (1, L=[(2,6-iPr2 C6 H3 )NC(Me)]2 ) with polyarenes afforded a series of mononuclear and dinuclear complexes: [LCo(η(4) -anthracene)] (2), [LCo(μ-η(4) :η(4) -naphthalene)CoL] (3), and [LCo(μ-η(4) :η(4) -phenanthrene)CoL] (4). The pyrene complexes [{Na2 (Et2 O)2 }{LCo(μ-η(3) :η(3) -pyrene)CoL}] (5) and [{Na2 (Et2 O)3 }{LCo(η(3) -pyrene)}] (6) were obtained by treating precursor 1 with pyrene followed by reduction with Na metal. These complexes contain three potential redox active centers: the cobalt metal and both α-diimine and polyarene ligands. Through a combination of X-ray crystallography, EPR spectroscopy, magnetic susceptibility measurement, and DFT computations, the electronic configurations of these complexes were studied. It was determined that complexes 2-4 have a high-spin Co(I) center coupled with a radical α-diimine ligand and a neutral polyarene ligand. Whereas, the ligand L in complexes 5 and 6 has been further reduced to the dianion, the cobalt remains in a formal (I) oxidation state, and the pyrene molecule is either neutral or monoanionic.
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