화학공학소재연구정보센터
Inorganic Chemistry, Vol.51, No.20, 10557-10571, 2012
Ligand Contributions to the Electronic Structures of the Oxidized Cobalt(II) salen Complexes
Square planar cobalt(II) complexes of salen ligands N,N'-bis(3-tert-butyl-5R-salicylidene)-1,2-cyclohexane-diamine), where R = OMe (1) and tert-butyl (2), were prepared. 1 and 2 were electrochemically reversibly oxidized into cations [1-H2O](+) and [2-H2O](+) in CH2Cl2. The chemically generated [1-H2O](SbF6)center dot 0.68 H2O center dot 0.82CH(2)Cl(2) and [2-H2O](SbF6)center dot 0.3H(2)O center dot 0.8SCH(2)Cl(2) were characterized by X-ray diffraction and NIR spectroscopy. Both complexes are paramagnetic species containing a square pyramidal cobalt ion coordinated at the apical position by an exogenous water molecule. They exhibit remarkable NIR bands at 1220 (7370 M-1 cm(-1)) and 1060 nm (5560 M-1 cm(-1)), respectively, assigned to a CT transition. DFT calculations and magnetic measurements confirm the paramagnetic (S = 1) ground spin state of the cations. They show that more than 70% of the total spin density in [1-H2O](+) and [2-H2O](+) is localized on the metal, the remaining spin density being distributed over the aromatic rings (30% phenoxyl character). In the presence of N-methylimidazole 1 and 2 are irreversibly oxidized by air into the genuine octahedral cobalt(III) bis(phenolate) complexes [1-im(2)](+) and [2-im(2)](+), the former being structurally characterized. Neither [1-im(2)](+) nor [2-im(2)](+) exhibits a NIR feature in its electronic spectrum. 1 and 2 were electrochemically two-electron oxidized into [1](2+) and [2](2+). The cations were identified as Co(III)-phenoxyl species by their characteristic absorption band at ca. 400 nm in the UV-vis spectrum. Coordination of the phenoxyl radical to the cobalt(III) metal ion is evidenced by the EPR signal centered at g = 2.00.