Dinuclear diphosphinecopper(I) complexes of the bis(chelating) S-frame ligand N2C(O)OCMe32 exhibit a remarkable kinetic and thermodn. stability of the deep blue o-semiquinonoid intermediate as evident from its facile formation, stability towards air and protic media, and from the electrochem. potential range. The comproportionation const. of CuI2μ-N2C(O)OCMe32μ-Ph2P(CH2)6PPh22+ was established at 1019.7. The crystal structure of the BPH4- salt was detd.: triclinic, space group P1̅, a 16.156(3), b 17.430(2), c 17.940(2) \AA, a 73.25(1), b 85.71(1), g 72.30(1)°, Z = 2, R = 0.119, R' = 0.132. It shows an inverse cryptate structure; 2 bridging diphosphine ligands span the 2 bridgehead Cu(I) centers which are fixed at 4.82 \AA apart by the bis(chelating) azodicarboxylate anion radical. In contrast to the neutral (reduced) form of the complex, the dicationic oxidized state could only be studied spectroelectrochem. on SciFinder(R)
%0 Journal Article
%1 Moscherosch.1993
%A Moscherosch, Michael
%A Field, John S.
%A Kaim, Wolfgang
%A Kohlmann, Stephan
%A Krejcik, Michael.
%D 1993
%J Journal of the Chemical Society, Dalton Transactions: Inorganic Chemistry
%K 1 azodiformate complex;comproportionation complex;crystal copper dinuclear semiquinonoid structure
%N 2
%P 211--216
%T 'Inverse cryptate' structure of an exceptionally stable dicopper(I) semiquinonoid intermediate
%X Dinuclear diphosphinecopper(I) complexes of the bis(chelating) S-frame ligand N2C(O)OCMe32 exhibit a remarkable kinetic and thermodn. stability of the deep blue o-semiquinonoid intermediate as evident from its facile formation, stability towards air and protic media, and from the electrochem. potential range. The comproportionation const. of CuI2μ-N2C(O)OCMe32μ-Ph2P(CH2)6PPh22+ was established at 1019.7. The crystal structure of the BPH4- salt was detd.: triclinic, space group P1̅, a 16.156(3), b 17.430(2), c 17.940(2) \AA, a 73.25(1), b 85.71(1), g 72.30(1)°, Z = 2, R = 0.119, R' = 0.132. It shows an inverse cryptate structure; 2 bridging diphosphine ligands span the 2 bridgehead Cu(I) centers which are fixed at 4.82 \AA apart by the bis(chelating) azodicarboxylate anion radical. In contrast to the neutral (reduced) form of the complex, the dicationic oxidized state could only be studied spectroelectrochem. on SciFinder(R)
@article{Moscherosch.1993,
abstract = {Dinuclear diphosphinecopper(I) complexes of the bis(chelating) S-frame ligand N2[C(O)OCMe3]2 exhibit a remarkable kinetic and thermodn. stability of the deep blue o-semiquinonoid intermediate as evident from its facile formation, stability towards air and protic media, and from the electrochem. potential range. The comproportionation const. of [CuI2{μ-N2[C(O)OCMe3]2}{μ-Ph2P(CH2)6PPh2}2]+ was established at 1019.7. The crystal structure of the BPH4- salt was detd.: triclinic, space group P1̅, a 16.156(3), b 17.430(2), c 17.940(2) {\AA}, \textgreek{a} 73.25(1), \textgreek{b} 85.71(1), \textgreek{g} 72.30(1)°, Z = 2, R = 0.119, R' = 0.132. It shows an inverse cryptate structure; 2 bridging diphosphine ligands span the 2 bridgehead Cu(I) centers which are fixed at 4.82 {\AA} apart by the bis(chelating) azodicarboxylate anion radical. In contrast to the neutral (reduced) form of the complex, the dicationic oxidized state could only be studied spectroelectrochem. [on SciFinder(R)]},
added-at = {2019-07-15T13:41:23.000+0200},
author = {Moscherosch, Michael and Field, John S. and Kaim, Wolfgang and Kohlmann, Stephan and Krejcik, Michael.},
biburl = {https://puma.ub.uni-stuttgart.de/bibtex/246e7abcdd0012be9ccfafe52e40716d2/b_schwederski},
interhash = {a3b0461d08c4e91aef07bb2a0c622b27},
intrahash = {46e7abcdd0012be9ccfafe52e40716d2},
issn = {0300-9246},
journal = {Journal of the Chemical Society, Dalton Transactions: Inorganic Chemistry},
keywords = {1 azodiformate complex;comproportionation complex;crystal copper dinuclear semiquinonoid structure},
number = 2,
pages = {211--216},
timestamp = {2019-07-15T11:42:10.000+0200},
title = {'Inverse cryptate' structure of an exceptionally stable dicopper(I) semiquinonoid intermediate},
year = 1993
}
