Syntheses and crystal structures of complexes [M2R2] [M = Cu, Ag, or Au; R = 2-C(SiMe3)2C5H 4N] and [cu4R′4] [r′ = 2-CH(SiMe3)C5H4N]; Electrochemical generation of [cu2R2]2+

Rocco I. Papasergio, Colin L. Raston, Allan H. White

Research output: Contribution to journalArticle

Abstract

Reaction of 'LiR,' where R = 2-C(SiMe3)2C 5H4N, with CuCl, AgBF4 or [Au(CO)Cl] in tetrahydrofuran-hexane yields binuclear complexes [M2R2] [M = Cu, (1); Ag, (2); Au, (3)] of relative thermal stabilities (1) > (3) > (2), the copper complex being sublimable in vacuo. In the same solvents, 'Li[2-CH(SiMe3)C5H4N]' yields a tetranuclear species [Cu4{2-CH(SiMe3)C5H4N} 4], (4), which rapidly decomposes in solution at ambient temperature to elemental copper. Electrochemistry reveals that (1) is reversibly oxidized to the formally copper(II) alkyl species [Cu2R2] 2+. The structures of complexes (1)-(4) have been established from single-crystal X-ray diffraction data. Molecules of (1)-(3) are centrosymmetric with each ligand bridging the two metal centres which are in close proximity [M ⋯ M 2.412(1) in (1), 2.654(1) in (2), and 2.672(1) Å in (3)]. In (4) the ligands bridge successive metal centres, alternating above and below a Cu4 square, M ⋯ M 2.668(2) Å.

Original languageEnglish
Pages (from-to)3085-3091
Number of pages7
JournalJournal of the Chemical Society, Dalton Transactions
Issue number12
DOIs
Publication statusPublished - Dec 1987
Externally publishedYes

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