Cis-MCl2(big), big = bis(1-methylimidazol-2-yl)glyoxal, M = Pt, Pd, were prepd. and characterized through electrochem., spectroscopy, and for M = Pt, by x-ray structure anal. The seven-membered chelate ring formed through N,N' coordination of the ligand big shows a boat conformation in agreement with d. functional theory (DFT) calcn. results. No significant intermol. interactions were obsd. for the platinum compd. Both the PdII and PtII complexes undergo reversible 1-electron redn. in CH2Cl2/0.1 M Bu4NPF6; the reduced palladium compd. disintegrates \textgreater-30°. EPR, UV-visible, and IR spectroelectrochem. studies were employed to study the monoanions. The anion radical complex cis-PtCl2(big).bul.- exhibits a well-resolved EPR spectrum with small but well-detectable g anisotropy and an isotropic 195Pt hyperfine coupling of 12.2 G. DFT calcns. confirm the spin concn. in the a-semidione part of the radical complex with small delocalization to the bis(imidazolyl)metal section. EPR and electroactive moieties can be linked to the cis-dichloroplatinum(II) group via imidazole coordination. on SciFinder(R)
%0 Journal Article
%1 Bulak.2007
%A Bulak, Ece
%A Leboschka, Markus
%A Schwederski, Brigitte
%A Sarper, Orkan
%A Varnali, Tereza
%A Fiedler, Jan
%A Lissner, Falk
%A Schleid, Thomas
%A Kaim, Wolfgang.
%D 2007
%J Inorganic Chemistry
%K chloro complex complex;methylimidazolyl crystal electrochem glyoxal methylimidazolyl palladium platinum prepn structure
%N 14
%P 5562--5566
%R 10.1021/ic070185b
%T Reversibly Reducible cis-Dichloroplatinum(II) and cis-Dichloropalladium(II) Complexes of Bis(1-methylimidazol-2-yl)glyoxal
%V 46
%X Cis-MCl2(big), big = bis(1-methylimidazol-2-yl)glyoxal, M = Pt, Pd, were prepd. and characterized through electrochem., spectroscopy, and for M = Pt, by x-ray structure anal. The seven-membered chelate ring formed through N,N' coordination of the ligand big shows a boat conformation in agreement with d. functional theory (DFT) calcn. results. No significant intermol. interactions were obsd. for the platinum compd. Both the PdII and PtII complexes undergo reversible 1-electron redn. in CH2Cl2/0.1 M Bu4NPF6; the reduced palladium compd. disintegrates \textgreater-30°. EPR, UV-visible, and IR spectroelectrochem. studies were employed to study the monoanions. The anion radical complex cis-PtCl2(big).bul.- exhibits a well-resolved EPR spectrum with small but well-detectable g anisotropy and an isotropic 195Pt hyperfine coupling of 12.2 G. DFT calcns. confirm the spin concn. in the a-semidione part of the radical complex with small delocalization to the bis(imidazolyl)metal section. EPR and electroactive moieties can be linked to the cis-dichloroplatinum(II) group via imidazole coordination. on SciFinder(R)
@article{Bulak.2007,
abstract = {Cis-MCl2(big), big = bis(1-methylimidazol-2-yl)glyoxal, M = Pt, Pd, were prepd. and characterized through electrochem., spectroscopy, and for M = Pt, by x-ray structure anal. The seven-membered chelate ring formed through N,N' coordination of the ligand big shows a boat conformation in agreement with d. functional theory (DFT) calcn. results. No significant intermol. interactions were obsd. for the platinum compd. Both the PdII and PtII complexes undergo reversible 1-electron redn. in CH2Cl2/0.1 M Bu4NPF6; the reduced palladium compd. disintegrates {\textgreater}-30°. EPR, UV-visible, and IR spectroelectrochem. studies were employed to study the monoanions. The anion radical complex [cis-PtCl2(big)].bul.- exhibits a well-resolved EPR spectrum with small but well-detectable g anisotropy and an isotropic 195Pt hyperfine coupling of 12.2 G. DFT calcns. confirm the spin concn. in the \textgreek{a}-semidione part of the radical complex with small delocalization to the bis(imidazolyl)metal section. EPR and electroactive moieties can be linked to the cis-dichloroplatinum(II) group via imidazole coordination. [on SciFinder(R)]},
added-at = {2022-06-15T11:26:56.000+0200},
author = {Bulak, Ece and Leboschka, Markus and Schwederski, Brigitte and Sarper, Orkan and Varnali, Tereza and Fiedler, Jan and Lissner, Falk and Schleid, Thomas and Kaim, Wolfgang.},
biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2d451817b77947b6a91a44f418188c203/huebleriac},
doi = {10.1021/ic070185b},
interhash = {f01899d21e0029cda6b3a47145f67b63},
intrahash = {d451817b77947b6a91a44f418188c203},
issn = {0020-1669},
journal = {Inorganic Chemistry},
keywords = {chloro complex complex;methylimidazolyl crystal electrochem glyoxal methylimidazolyl palladium platinum prepn structure},
number = 14,
pages = {5562--5566},
timestamp = {2022-06-15T09:26:56.000+0200},
title = {Reversibly Reducible cis-Dichloroplatinum(II) and cis-Dichloropalladium(II) Complexes of Bis(1-methylimidazol-2-yl)glyoxal},
volume = 46,
year = 2007
}