"(alpha-Diimine)tricarbonylhalorhenium complexes: the oxidation side"@en . "Kaim, W." . . . "121736" . . "3" . "Bubrin, M." . . "1477-9226" . "(alpha-Diimine)tricarbonylhalorhenium complexes: the oxidation side" . "000298753800041" . . . . "The electrochemical behaviour of the complexes [Re(CO)(3)X(alpha-diimine)], X = Cl or Br, alpha-diimine = 1,4-di-tert-butyl-1,4-diaza-1,3-diene, was reinvestigated using cyclic voltammetry accompanied by IR and UV-vis spectroelectrochemistry. While the reduction results in the loss of halide, as necessary for the electrocatalytic activity of related diimine compounds, a reversible oxidation could be observed for the chloro complex 1 (X = Cl). The conversion of 1 to 1(+) in CH2Cl2 or CH3CN is accompanied by high-frequency shifts (Delta v = 73-114 cm (1)) of the three carbonyl stretching bands, by a considerable change in carbonyl stretching modes, and by changed absorption in the visible region. DFT calculations support the spectroelectrochemical results and suggest an unusually large g anisotropy (g(1) 1.38, g(2) 2.06, g(3) 3.20) which explains the absence of detectable EPR signals for 1(+) under normal X band conditions. Frontier orbitals calculated by DFT for 1 reveal two close lying occupied orbitals (HOMO, HOMO-1) with Re-Cl character and a diimine based LUMO." . "7"^^ . "2"^^ . . "[052E4A0E996C]" . "Drozdz, A." . "Z\u00E1li\u0161, Stanislav" . . . "Fiedler, Jan" . "RIV/61388955:_____/12:00375976" . "The electrochemical behaviour of the complexes [Re(CO)(3)X(alpha-diimine)], X = Cl or Br, alpha-diimine = 1,4-di-tert-butyl-1,4-diaza-1,3-diene, was reinvestigated using cyclic voltammetry accompanied by IR and UV-vis spectroelectrochemistry. While the reduction results in the loss of halide, as necessary for the electrocatalytic activity of related diimine compounds, a reversible oxidation could be observed for the chloro complex 1 (X = Cl). The conversion of 1 to 1(+) in CH2Cl2 or CH3CN is accompanied by high-frequency shifts (Delta v = 73-114 cm (1)) of the three carbonyl stretching bands, by a considerable change in carbonyl stretching modes, and by changed absorption in the visible region. DFT calculations support the spectroelectrochemical results and suggest an unusually large g anisotropy (g(1) 1.38, g(2) 2.06, g(3) 3.20) which explains the absence of detectable EPR signals for 1(+) under normal X band conditions. Frontier orbitals calculated by DFT for 1 reveal two close lying occupied orbitals (HOMO, HOMO-1) with Re-Cl character and a diimine based LUMO."@en . "RIV/61388955:_____/12:00375976!RIV13-AV0-61388955" . . "5"^^ . . "(alpha-Diimine)tricarbonylhalorhenium complexes: the oxidation side" . . . "10.1039/c1dt11449b" . . "Dalton Transactions" . "41" . "GB - Spojen\u00E9 kr\u00E1lovstv\u00ED Velk\u00E9 Brit\u00E1nie a Severn\u00EDho Irska" . . . "P(LD11086), P(ME10124), Z(AV0Z40400503)" . . . "(alpha-Diimine)tricarbonylhalorhenium complexes: the oxidation side"@en . "(alpha-Diimine)tricarbonylhalorhenium complexes; electrochemistry; metal carbonyl complexes"@en . .