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'Inverse Cryptate' Structure of an Exceptionally Stable Dicopper(I) Semiquinonoid Intermediate

DOI: 10.1039/DT9930000211

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Journal of the Chemical Society, Dalton Transactions p. 211 - 217 (1993)

Update date:2022-09-26

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Authors:

Moscherosch, MichaelMoscherosch, Michael

Field, John S.Field, John S.

Kaim, WolfgangKaim, Wolfgang

Kohlmann, StephanKohlmann, Stephan

Krejcik, MichaelKrejcik, Michael

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Article abstract of DOI:10.1039/DT9930000211

Dinuclear diphosphinecopper(I) complexes of the bis(chelating) 'S-frame' ligand di-tert-butyl azodiformate exhibit a remarkable kinetic and thermodynamic stability of the deep blue o-semiquinonoid intermediate as evident from its facile formation, stability towards air and protic media, and from the electrochemical potential range.The comproportionation constant of t)>2><μ-Ph2P(CH2)6PPh2>2>(1+) was established at 1019.7.The crystal structure of the tetraphenylborate salt has been determined.It shows an 'inverse cryptate' structure; two bridging diphosphine ligands span the two bridgehead copper(I) centres which are fixed at 4.82 Angstroem apart by the bis(chelating) azodicarboxylate anion radical.In contrast to the neutral (reduced) form of the complex, the dicationic oxidised state could only be studied spectroelectrochemically.

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