%0 Journal Article %1 Stange.1995 %A Stange, Andreas F. %A Waldhoer, Eberhard %A Moscherosch, Michael %A Kaim, Wolfgang. %D 1995 %J Zeitschrift fuer Naturforschung, B: A Journal of Chemical Sciences %K complex complex;thiolate copper crystal deriv dimethylphenanthroline dinuclear phenanthroline structure toluene toluenethiolate;electrochem %N 1 %P 115--122 %R 10.1515/znb-1995-0122 %T Variable structure of the Cu2S2 core in doubly thiolate-bridged dicopper(I) complexes. An x-ray crystallographic, electrochemical and EPR study of (dmp)2(o-CH3C6H4S)2Cu2, dmp = 2,9-dimethyl-1,10-phenanthroline, and a comment on the nature of phenanthroline-containing \dqCu(0)\dq complexes %V 50 %X The mol. and crystal structure of the dicopper(I) complex (dmp)2(m-o-CH3C6H4S)2Cu2 (1), dmp = 2,9-dimethyl-1,10-phenanthroline, was detd. With Cu/S/Cu and S/Cu/S bond angles between 80 and 100°, the planar structure of the central CuSCuS four-membered ring is much more sym. for 1 as compared to the analogous complex 2 of unsubstituted 1,10-phenanthroline which has a folded Cu2S2 core with bond angles between 67 and 108°. This result illustrates a considerable structural flexibility of the LCu(m-SR)2CuL entity which is being discussed as a possible model for CuA centers of cytochrome c oxidase or nitrous oxide reductase. Oxidn. of both complexes 1 and 2 remains irreversible even at cyclovoltammetric scan rates of 1 V/s. However, the Me substitution in complex 1 causes increased reversibility of the electronically coupled dmp-based redn. processes. Accordingly, the EPR spectrum of 1.bul.- was characterized by hyperfine splitting from dmp.bul.- and a relatively small 63,65Cu coupling of 0.53 mT. The stabilization of 2,9-disubstituted 1,10-phenanthroline radical anions by coordination to Cu(I) is also demonstrated by detection of a single broad EPR line at g 2.0028 for the formal Cu(0) complex Cu(dpp)2 = CuI(dpp.bul.0)(dpp), dpp = 2,9-diphenyl-1,10-phenanthroline. While the EPR signal of Cu(dpp)2 loses intensity on cooling, possibly due to dimerization and spin-pairing, the distorted tetrahedral configuration with essential orthogonal arrangement of dpp p systems seems to disfavor an intramol. electron hopping. on SciFinder(R)

@article{Stange.1995, abstract = {The mol. and crystal structure of the dicopper(I) complex (dmp)2(\textgreek{m}-o-CH3C6H4S)2Cu2 (1), dmp = 2,9-dimethyl-1,10-phenanthroline, was detd. With Cu/S/Cu and S/Cu/S bond angles between 80 and 100°, the planar structure of the central CuSCuS four-membered ring is much more sym. for 1 as compared to the analogous complex 2 of unsubstituted 1,10-phenanthroline which has a folded Cu2S2 core with bond angles between 67 and 108°. This result illustrates a considerable structural flexibility of the LCu(\textgreek{m}-SR)2CuL entity which is being discussed as a possible model for CuA centers of cytochrome c oxidase or nitrous oxide reductase. Oxidn. of both complexes 1 and 2 remains irreversible even at cyclovoltammetric scan rates of 1 V/s. However, the Me substitution in complex 1 causes increased reversibility of the electronically coupled dmp-based redn. processes. Accordingly, the EPR spectrum of 1.bul.- was characterized by hyperfine splitting from dmp.bul.- and a relatively small 63,65Cu coupling of 0.53 mT. The stabilization of 2,9-disubstituted 1,10-phenanthroline radical anions by coordination to Cu(I) is also demonstrated by detection of a single broad EPR line at g 2.0028 for the formal Cu(0) complex Cu(dpp)2 = CuI(dpp.bul.0)(dpp), dpp = 2,9-diphenyl-1,10-phenanthroline. While the EPR signal of Cu(dpp)2 loses intensity on cooling, possibly due to dimerization and spin-pairing, the distorted tetrahedral configuration with essential orthogonal arrangement of dpp \textgreek{p} systems seems to disfavor an intramol. electron hopping. [on SciFinder(R)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Stange, Andreas F. and Waldhoer, Eberhard and Moscherosch, Michael and Kaim, Wolfgang.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2efe13978a11dbdc48a015f503644792b/huebleriac}, doi = {10.1515/znb-1995-0122}, interhash = {c605487c2619341d4d218f3d8b59ef3d}, intrahash = {efe13978a11dbdc48a015f503644792b}, issn = {0932-0776}, journal = {Zeitschrift fuer Naturforschung, B: A Journal of Chemical Sciences}, keywords = {complex complex;thiolate copper crystal deriv dimethylphenanthroline dinuclear phenanthroline structure toluene toluenethiolate;electrochem}, number = 1, pages = {115--122}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {Variable structure of the Cu2S2 core in doubly thiolate-bridged dicopper(I) complexes. An x-ray crystallographic, electrochemical and EPR study of (dmp)2(o-CH3C6H4S)2Cu2, dmp = 2,9-dimethyl-1,10-phenanthroline, and a comment on the nature of phenanthroline-containing {\dq}Cu(0){\dq} complexes}, volume = 50, year = 1995 }