'Inverse cryptate' structure of an exceptionally stable dicopper(I) semiquinonoid intermediate

, , , , und . Journal of the Chemical Society, Dalton Transactions: Inorganic Chemistry (1993)


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)

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