Abstract
The electrochem. behavior of Re(CO)3X(a-diimine), X = Cl or Br, a-diimine = 1,4-di-tert-butyl-1,4-diaza-1,3-diene, was restudied using cyclic voltammetry accompanied by IR and UV-visible spectroelectrochem. While the redn. results in the loss of halide, as necessary for the electrocatalytic activity of related diimine compds., a reversible oxidn. could be obsd. for the chloro complex 1 (X = Cl). The conversion of 1 to 1+ in CH2Cl2 or MeCN is accompanied by high-frequency shifts (Dn = 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 calcns. support the spectroelectrochem. results and suggest an unusually large g anisotropy (g1 1.38, g2 2.06, g3 3.20) which explains the absence of detectable EPR signals for 1+ under normal X band conditions. Frontier orbitals calcd. by DFT for 1 reveal two close lying occupied orbitals (HOMO, HOMO-1) with Re-Cl character and a diimine based LUMO. on SciFinder(R)
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