N. Weidemann, Grant W. Margulieux, C. Moore
Dec 15, 2010
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Influential Citations
7
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Journal
Inorganica Chimica Acta
Abstract
Detailed herein are synthetic, spectroscopic and structural studies on trisisocyanide cobalt halide complexes featuring the encumbering m -terphenyl isocyanide CNAr Mes2 (Mes = 2,4,6-Me 3 C 6 H 3 ). Addition of CNAr Mes2 to CoI 2 in a 3:1 molar ratio provides the mononuclear complex, CoI 2 (CNAr Mes2 ) 3 , which can be oxidized to six-coordinate CoI 3 (CNAr Mes2 ) 3 upon treatment with 0.5 equivalents of I 2 . Contrastingly, addition of CNAr Mes2 to CoBr 2 provided the dinuclear complex Br 2 Co(μ 2 -Br) 2 Co(CNAr Mes2 ) 3 irrespective of the molar ratios employed. FTIR analysis on these Co(II) and Co(III) complexes is used to assess the relative π-basicities of the cobalt centers toward the CNAr Mes2 ligands. Treatment of CoX 2 (X = Cl, Br and I) with three CNAr Mes2 ligands followed by the addition of granulated Zn provides the pseudo-tetrahedral complexes XCo(CNAr Mes2 ) 3 . FTIR, magnetic and X-ray crystallographic studies are used to determine both the ground state electronic structure and relative π-basicities of these complexes.