Syntheses and structures of some complexes containing M3(μ-dppm)3 moieties (M = Cu, Ag) linking C4M′Lx groups [M′Lx = Re(CO)3(But 2-bpy), Ru(dppe)Cp∗]

Autor: B. Le Guennic, H. Sahnoune, N. Scoleri, Christopher J. Sumby, N.N. Zaitseva, Jean-François Halet, B.G. Ellis, Brian W. Skelton, Alexandre N. Sobolev, Brian K. Nicholson, Allan H. White, M.I. Bruce
Přispěvatelé: University of South Australia [Adelaide], Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), University of Waikato [Hamilton], The University of Western Australia (UWA), ARC, Australian Research Council, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Jazyk: angličtina
Rok vydání: 2016
Předmět:
Zdroj: Inorganica Chimica Acta
Inorganica Chimica Acta, Elsevier, 2016, 453, pp.654--666. ⟨10.1016/j.ica.2016.09.017⟩
Inorganica Chimica Acta, 2016, 453, pp.654--666. ⟨10.1016/j.ica.2016.09.017⟩
ISSN: 0020-1693
DOI: 10.1016/j.ica.2016.09.017⟩
Popis: Reactions between [Ru(Ctriple bond; length of mdashCCtriple bond; length of mdashCH)(dppe)Cp∗] and [M2(NCMe)x(dppm)2]2+ (M = Cu, x = 4; Ag, x = 2) have given complexes containing M3(μ-dppm)3 clusters attached to one or two single bondCtriple bond; length of mdashCCtriple bond; length of mdashC[Ru(dppe)Cp∗] groups. Single crystal X-ray studies are recorded for [{M3(μ-dppm)3}{μ3-Ctriple bond; length of mdashCCtriple bond; length of mdashC[Ru(dppe)Cp∗]}](BF4)2·nS (M = Cu, Ag) [isomorphous (orthorhombic) for S = (ill-defined) acetone]. A different (triclinic) polymorph has also been defined for M = Ag, nS = 5THF. Together with [{Cu3(μ-dppm)3}{μ3-Ctriple bond; length of mdashCCtriple bond; length of mdashC[Ru(dppe)Cp∗]}2]PF6·4Me2CO, the structures definitively confirm the complexes as clear examples of mono- or bis-diyndiyl-M3 systems, devoid of close approaches to the vacant M3 faces of the former by counterions in the case of their acetone solvates, except in the case of the BF4 counterion in the AgBF4/thf solvate. Cyclic voltammetric studies suggest that there are only weak electronic interactions between the ruthenium centres in the bis(diynyl) complexes, consequent upon weak overlaps between the carbon chain and the M3(μ-dppm)3 clusters, as confirmed by DFT calculations on model complexes [{M3(μ-dHpm)3}{Ctriple bond; length of mdashCCtriple bond; length of mdashC[Ru(dHpe)Cp]}n]3-n [n = 1, 2; dHpm = CH2(PH2)2, dHpe = H2P(CH2)2PH2]. The complexes [Ag3Cl2(dppm)3]PF6, [M3(μ-dppm)3(X){μ3-Ctriple bond; length of mdashCCtriple bond; length of mdashC[Re(CO)3(But2-bpy)]}]PF6 (M = Cu, X = Ctriple bond; length of mdashCCtriple bond; length of mdashC[Re(CO)3(But2-bpy)]; M = Ag; X = Cl), [Ag6(μ-dppm)4{Ctriple bond; length of mdashCCtriple bond; length of mdashC[Re(CO)3(But2-bpy)]}4](PF6)2 have also been prepared and structurally characterised. In the M3 clusters, some asymmetry in the attachment of at least one of the μ3 ligands is apparent, which results from interactions with solvate molecules.
Databáze: OpenAIRE
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