Triple-decker cationic complexes with a central pentaphospholyl (pentaphosphacyclopentadienyl) ligand [Cp*M(μ-η:η-P5)M′ (η-C5R5)]+ (3b: M = M′= Fe, R = Me; 4a: M = Ru, M′= Fe, R = H; 4b: M = Fe, M′= Ru, R = H; 4c: M = Fe, M′= Ru, R = Me; 5a: M = M′= Ru, R = H; 5b: M = M′= Ru, R = Me) were synthesized by exploitation of the stacking reactions of pentaphosphametallocenes Cp*M(η-P5) (1: M = Fe; 2: M = Ru) with half-sandwich fragments [(η-C5R5)M′]+. They were isolated as salts with BF4- or PF6- anions, and the structures of 4aPF6 and 5bPF6 were determined by X-ray diffraction. Triple-decker complexes with a central pentaphospholyl ligand are less reactive in nucleophilic degradation reactions than analogous complexes with C4Me4P and Cp* ligands in the bridging position. Only 4a and the previously known analogue 3a (M = M′ = Fe, R = H), containing the CpFe fragment, are nucleophilically destroyed by MeCN and Nal. The electrochemical properties of 2, 3a, 3b, 4a-c, 5a and 5b and the related cobalt-containing complexes [(η-C4Me4)Co([μ-η:η- P5)MCp*]+ (6: M = Fe; 7: M = Ru) were investigated. © Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002.
Kudinov, A.R., Loginov, D.A., Starikova, Z.A., Petrovskii, P.V., Corsini, M., Zanello, P. (2002). Iron- and ruthenium-containing triple-decker complexes with a central pentaphospholyl ligand - X-ray structures of [(η-C5H5)Fe(μ-η: η-P5)Ru(η-C5Me5)]PF6 and [(η-C5Me5)Ru(μ-η: η-P5)Ru(η-C5Me5)]PF6. EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2002(11), 3018-3027 [10.1002/1099-0682(200211)2002:11<3018::AID-EJIC3018>3.0.CO;2-A].
Iron- and ruthenium-containing triple-decker complexes with a central pentaphospholyl ligand - X-ray structures of [(η-C5H5)Fe(μ-η: η-P5)Ru(η-C5Me5)]PF6 and [(η-C5Me5)Ru(μ-η: η-P5)Ru(η-C5Me5)]PF6
Corsini M.;Zanello P.
2002-01-01
Abstract
Triple-decker cationic complexes with a central pentaphospholyl (pentaphosphacyclopentadienyl) ligand [Cp*M(μ-η:η-P5)M′ (η-C5R5)]+ (3b: M = M′= Fe, R = Me; 4a: M = Ru, M′= Fe, R = H; 4b: M = Fe, M′= Ru, R = H; 4c: M = Fe, M′= Ru, R = Me; 5a: M = M′= Ru, R = H; 5b: M = M′= Ru, R = Me) were synthesized by exploitation of the stacking reactions of pentaphosphametallocenes Cp*M(η-P5) (1: M = Fe; 2: M = Ru) with half-sandwich fragments [(η-C5R5)M′]+. They were isolated as salts with BF4- or PF6- anions, and the structures of 4aPF6 and 5bPF6 were determined by X-ray diffraction. Triple-decker complexes with a central pentaphospholyl ligand are less reactive in nucleophilic degradation reactions than analogous complexes with C4Me4P and Cp* ligands in the bridging position. Only 4a and the previously known analogue 3a (M = M′ = Fe, R = H), containing the CpFe fragment, are nucleophilically destroyed by MeCN and Nal. The electrochemical properties of 2, 3a, 3b, 4a-c, 5a and 5b and the related cobalt-containing complexes [(η-C4Me4)Co([μ-η:η- P5)MCp*]+ (6: M = Fe; 7: M = Ru) were investigated. © Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
https://hdl.handle.net/11365/1144350
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