(alpha-Diimine)tricarbonylhalorhenium complexes: the oxidation side

0375976 - ÚFCH JH 2013 RIV GB eng J - Článek v odborném periodiku
Drozdz, A. - Bubrin, M. - Fiedler, Jan - Záliš, Stanislav - Kaim, W.
(alpha-Diimine)tricarbonylhalorhenium complexes: the oxidation side.
Dalton Transactions. Roč. 41, č. 3 (2012), s. 1013-1019. ISSN 1477-9226. E-ISSN 1477-9234
Grant CEP: GA MŠMT LD11086; GA MŠMT(CZ) ME10124
Výzkumný záměr: CEZ:AV0Z40400503
Klíčová slova: (alpha-Diimine)tricarbonylhalorhenium complexes * electrochemistry * metal carbonyl complexes
Kód oboru RIV: CG - Elektrochemie
Impakt faktor: 3.806, rok: 2012

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.
Trvalý link: http://hdl.handle.net/11104/0208498