New Cu(i) and Ag(i) binuclear complexes containing the dppa ligand
- 30 October 2002
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 23,p. 4365-4374
- https://doi.org/10.1039/b205922n
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.This publication has 43 references indexed in Scilit:
- Syntheses and Crystal Structures of Polynuclear Cu(I) Complexes Containing the 1,1′-Bis-(diphenylphosphino)-ferrocene LigandMonatshefte für Chemie / Chemical Monthly, 2000
- Homoleptic complexes of Ag(I), Cu(I), Pd(II) and Pt(II) with tetrathiafulvalene-functionalized phosphine ligands †J. Chem. Soc., Dalton Trans., 2000
- A Copper(I) Oxygenation Precursor in the Entatic State: Two Isomers of a Copper(I) Compound of a Rigid Tetradentate LigandChemistry – A European Journal, 2000
- Bis[μ-methylenebis(diphenylphosphine)-P:P']disilver(I) Diperchlorate Bis(dichloromethane) SolvateActa Crystallographica Section C Crystal Structure Communications, 1998
- The accuracy of the pseudopotential approximation. II. A comparison of various core sizes for indium pseudopotentials in calculations for spectroscopic constants of InH, InF, and InClThe Journal of Chemical Physics, 1996
- Synthesis, Structure, Photophysics, and Excited‐State Redox Properties of the Novel Luminescent Tetranuclear Acetylidocopper(I) Complex [Cu4(μ‐dppm)4(μ4‐η1,η2‐CC‐)](BF4)2Angewandte Chemie International Edition in English, 1996
- P–N–S/Se-containing metallacyclesJ. Chem. Soc., Dalton Trans., 1996
- Energy-adjusted pseudopotentials for the actinides. Parameter sets and test calculations for thorium and thorium monoxideThe Journal of Chemical Physics, 1994
- MO theory made visibleJournal of Chemical Education, 1990
- Imidodiphosphinatometal Chelates, Neutral Complexes with Carbon-Free Chelate RingsAngewandte Chemie International Edition in English, 1964