Two (cAAC)2Cu (cAAC = cyclic (alkyl)(amino)carbene) complexes, featuring a two-coordinate Cu atom in the formal oxidn. state zero, were prepd. by reducing (Et2-cAAC)2Cu+I- with metallic Na in THF, and by a 1-pot synthesis using Me2-cAAC, Cu(II)Cl2, and KC8 in toluene in a molar ratio of 2:1:2, resp. Both complexes are highly air and moisture sensitive but can be stored in the solid state for a month at room temp. DFT calcns. showed that in these complexes the Cu center has a d10 electronic configuration and the unpaired electron is delocalized over two carbene C atoms. This was further confirmed by the EPR spectra, which exhibit multiple hyperfine lines due to the coupling of the unpaired electron with 63,65Cu isotopes, 14N, and 1H nuclei. on SciFinder(R)
%0 Journal Article
%1 Weinberger.2014
%A Weinberger, David S.
%A Amin SK, Nurul
%A Mondal, Kartik Chandra
%A Melaimi, Mohand
%A Bertrand, Guy
%A Stuckl, A. Claudia
%A Roesky, Herbert W.
%A Dittrich, Birger
%A Demeshko, Serhiy
%A Schwederski, Brigitte
%A Kaim, Wolfgang
%A Jerabek, Paul
%A Frenking, Gernot.
%D 2014
%J Journal of the American Chemical Society
%K ESR cAAC copper crystal electrochem mol oxidn prepn prepn;mol prepn;optimized pyrrolidinylidene state structure zero
%N 17
%P 6235--6238
%R 10.1021/ja502521b
%T Isolation of Neutral Mononuclear Copper Complexes Stabilized by Two Cyclic (Alkyl)(amino)carbenes
%V 136
%X Two (cAAC)2Cu (cAAC = cyclic (alkyl)(amino)carbene) complexes, featuring a two-coordinate Cu atom in the formal oxidn. state zero, were prepd. by reducing (Et2-cAAC)2Cu+I- with metallic Na in THF, and by a 1-pot synthesis using Me2-cAAC, Cu(II)Cl2, and KC8 in toluene in a molar ratio of 2:1:2, resp. Both complexes are highly air and moisture sensitive but can be stored in the solid state for a month at room temp. DFT calcns. showed that in these complexes the Cu center has a d10 electronic configuration and the unpaired electron is delocalized over two carbene C atoms. This was further confirmed by the EPR spectra, which exhibit multiple hyperfine lines due to the coupling of the unpaired electron with 63,65Cu isotopes, 14N, and 1H nuclei. on SciFinder(R)
@article{Weinberger.2014,
abstract = {Two (cAAC)2Cu (cAAC = cyclic (alkyl)(amino)carbene) complexes, featuring a two-coordinate Cu atom in the formal oxidn. state zero, were prepd. by reducing (Et2-cAAC)2Cu+I- with metallic Na in THF, and by a 1-pot synthesis using Me2-cAAC, Cu(II)Cl2, and KC8 in toluene in a molar ratio of 2:1:2, resp. Both complexes are highly air and moisture sensitive but can be stored in the solid state for a month at room temp. DFT calcns. showed that in these complexes the Cu center has a d10 electronic configuration and the unpaired electron is delocalized over two carbene C atoms. This was further confirmed by the EPR spectra, which exhibit multiple hyperfine lines due to the coupling of the unpaired electron with 63,65Cu isotopes, 14N, and 1H nuclei. [on SciFinder(R)]},
added-at = {2019-07-15T13:41:23.000+0200},
author = {Weinberger, David S. and {Amin SK}, Nurul and Mondal, Kartik Chandra and Melaimi, Mohand and Bertrand, Guy and Stuckl, A. Claudia and Roesky, Herbert W. and Dittrich, Birger and Demeshko, Serhiy and Schwederski, Brigitte and Kaim, Wolfgang and Jerabek, Paul and Frenking, Gernot.},
biburl = {https://puma.ub.uni-stuttgart.de/bibtex/26b99c93e660a9dee23a401548f478a87/b_schwederski},
doi = {10.1021/ja502521b},
interhash = {39917d17be87c35f660259275caa5849},
intrahash = {6b99c93e660a9dee23a401548f478a87},
issn = {0002-7863},
journal = {Journal of the American Chemical Society},
keywords = {ESR cAAC copper crystal electrochem mol oxidn prepn prepn;mol prepn;optimized pyrrolidinylidene state structure zero},
number = 17,
pages = {6235--6238},
timestamp = {2019-07-15T11:42:10.000+0200},
title = {Isolation of Neutral Mononuclear Copper Complexes Stabilized by Two Cyclic (Alkyl)(amino)carbenes},
volume = 136,
year = 2014
}
