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)
%0 Journal Article
%1 Drozdz.2012
%A Drozdz, Anita
%A Bubrin, Martina
%A Fiedler, Jan
%A Zalis, Stanislav
%A Kaim, Wolfgang.
%D 2012
%J Dalton Transactions
%K carbonyl chloro;rhenium crystal diimine electrochem electronic halo rhenium structure
%N 3
%P 1013--1019
%R 10.1039/C1DT11449B
%T (a-Diimine)tricarbonylhalorhenium complexes: The oxidation side
%V 41
%X 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)
@article{Drozdz.2012,
abstract = {The electrochem. behavior of [Re(CO)3X(\textgreek{a}-diimine)], X = Cl or Br, \textgreek{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 (\textgreek{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)]},
added-at = {2022-06-15T11:26:56.000+0200},
author = {Drozdz, Anita and Bubrin, Martina and Fiedler, Jan and Zalis, Stanislav and Kaim, Wolfgang.},
biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2216c7314824b3f32e95c19086f4ec918/huebleriac},
doi = {10.1039/C1DT11449B},
interhash = {30fdb0c3063519679153f7a3f8cb7e8c},
intrahash = {216c7314824b3f32e95c19086f4ec918},
issn = {1477-9226},
journal = {Dalton Transactions},
keywords = {carbonyl chloro;rhenium crystal diimine electrochem electronic halo rhenium structure},
number = 3,
pages = {1013--1019},
timestamp = {2022-06-15T09:26:56.000+0200},
title = {(\textgreek{a}-Diimine)tricarbonylhalorhenium complexes: The oxidation side},
volume = 41,
year = 2012
}