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

Warning

This publication doesn't include Faculty of Arts. It includes Faculty of Science. Official publication website can be found on muni.cz.

Authors	LIU H. Z. CALHORDA M. J. DREW M. G. B. FELIX V. NOVOSAD J. VEIROS L. F. DE BIANI F. F. ZANELLO P.
Year of publication	2002
Type	Article in Periodical
Magazine / Source	J. Chem. Soc., Dalton Trans.
MU Faculty or unit	Faculty of Science
Citation
Field	Inorganic chemistry
Keywords	MOLECULAR-ORBITAL METHODS; EFFECTIVE CORE POTENTIALS; GAUSSIAN-TYPE BASIS; METAL-METAL BONDS; POLARIZATION FUNCTIONS; BASIS-SETS; ORGANIC-MOLECULES; CRYSTAL; COPPER(I); EQUILIBRIUM
Description	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(dppaO(2))(3)][PF6], 1. In an inert atmosphere, the binuclear complexes [Cu-2(dppa)(2)(NCCH3)(3)][PF6](2), 2, [Cu-2(dppa)(2)(NCCH3)(4)][PF6](2), 3, [Ag-2(dppa)(2)(NCCH3)(2)][PF6](2), 4, and [Ag-2(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 [M-2(dppa)(2)(NCCH3)(x)](n+) complexes, including the 0.47 Angstrom increase in M ... M distance upon going from 2 to 3.
Related projects:	Crystal structures and bonding in non-metal compounds of the V., VI. , and VII. group of the periodic systém Synthesis ,structure and bonding of compounds containing phosphorus,nitrogen,chalcogene and/or halogene atoms Structure and character of bonding, properties and analysis of synthetic and natural molecular ensembles