Issue 23, 2002
From the journal:

Journal of the Chemical Society, Dalton Transactions

New Cu(i) and Ag(i) binuclear complexes containing the dppa ligand

Huizhang Liu,a   Maria José Calhorda,ab   Michael G. B. Drew,c   Vitor Félix,d   Josef Novosad,e   Luís F. Veiros,f   Fabrizia Fabrizi de Bianig  and  Piero Zanellog  

a Instituto de Tecnologia Química e Biológica (ITQB), Av. da República, EAN, Apt 127, 2781-901 Oeiras, Portugal
E-mail: mjc@itqb.unl.pt

b Departamento de Química e Bioquímica, Faculdade de Ciências da Universidade de Lisboa, 1749-016 Lisboa, Portugal

c Department of Chemistry, University of Reading, Whiteknights, Reading, UK

d Departamento de Química, Universidade de Aveiro, 3810-193 Aveiro, Portugal

e Department of Inorganic Chemistry, Faculty of Science, Masaryk University, Kotlárska 2, 611 37 Brno, Czech Republic

f Centro de Química Estrutural, Complexo I, Instituto Superior Técnico, Av. Rovisco Pais, 1, 1049-001 Lisboa, Portugal

g Chemistry Department, University of Siena, Via Aldo Moro, I-43100, Italy

Abstract

New Cu(I) and Ag(I) binuclear complexes were prepared by reaction of [M(NCCH3)4][PF6] (M = Ag, Cu) with the bidentate phosphine ligands Ph2PNHPPh2 (dppa) and Ph2PCH2PPh2 (dppm). In the reaction of Cu(I) with dppa the phosphine is easily oxidized to give the octahedral species of [Cu(dppaO2)3][PF6], 1. In an inert atmosphere, the binuclear complexes [Cu2(dppa)2(NCCH3)3][PF6]2, 2, [Cu2(dppa)2(NCCH3)4][PF6]2, 3, [Ag2(dppa)2(NCCH3)2][PF6]2, 4, and [Ag2(dppm)2][PF6]2, 5, were formed and structurally characterized by X-ray diffraction (except for 5). The electrochemical studies showed that the most relevant property of the binuclear species was the ease of forming the metal upon reduction. EH and DFT calculations were performed in order to try and understand the structural features of the [M2(dppa)2(NCCH3)x]n+ complexes, including the 0.47 Å increase in M⋯M distance upon going from 2 to 3.

Graphical abstract: New Cu(i) and Ag(i) binuclear complexes containing the dppa ligand

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Article information

DOI
https://doi.org/10.1039/B205922N
Article type
Paper
Submitted
05 Sep 2002
Accepted
24 Sep 2002
First published
30 Oct 2002

J. Chem. Soc., Dalton Trans., 2002, 4365-4374

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New Cu(I) and Ag(I) binuclear complexes containing the dppa ligand

H. Liu, M. José Calhorda, M. G. B. Drew, V. Félix, J. Novosad, L. F. Veiros, F. Fabrizi de Biani and P. Zanello, J. Chem. Soc., Dalton Trans., 2002, 4365 DOI: 10.1039/B205922N

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