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• W1979702960 endingPage "4724" @default.
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• W1979702960 abstract "Abstract The arylation of [VCl 3 (thf) 3 ] with LiR Cl , where R Cl is a polychlorinated phenyl group [C 6 Cl 5 , 2,4,6‐trichlorophenyl(tcp), or 2,6‐dichlorophenyl (dcp)] gives four‐coordinate, homoleptic organovanadium( III ) derivatives with the formula [Li(thf) 4 ][V III (R Cl ) 4 ] (R Cl =C 6 Cl 5 ( 1 ), tcp ( 2 ), dcp ( 3 )). The anion [V III (C 6 Cl 5 ) 4 ] − has an almost tetrahedral geometry, as observed in the solid‐state structure of [NBu 4 ][V(C 6 Cl 5 ) 4 ] ( 1′ ) (X‐ray diffraction). Compounds 1 – 3 are electrochemically related to the neutral organovanadium( IV ) species [V IV (R Cl ) 4 ] (R Cl =C 6 Cl 5 ( 4 ), tcp ( 5 ), dcp ( 6 )). The redox potentials of the V IV /V III semisystems in CH 2 Cl 2 decrease with decreasing chlorination of the phenyl ring ( E 1/2 =0.84 ( 4 / 1 ), 0.42 ( 5 / 2 ), 0.25 V ( 6 / 3 )). All the [V IV (R Cl ) 4 ] derivatives involved in these redox couples could also be prepared and isolated by chemical methods. The arylation of [VCl 3 (thf) 3 ] with LiC 6 F 5 also gives a homoleptic organovanadium( III ) compound, but with a different stoichiometry: [NBu 4 ] 2 [V III (C 6 F 5 ) 5 ] ( 7 ). In this five‐coordinate species, the C 6 F 5 groups define a trigonal bipyramidal environment for the vanadium atom (X‐ray diffraction). EPR spectra for the new organovanadium compounds 1 – 6 are also given and analysed in terms of an elongated tetrahedral structure with C 2 v local symmetry. It is suggested that the R Cl groups exert a protective effect towards the vanadium centre." @default.
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• W1979702960 date "2005-07-25" @default.
• W1979702960 modified "2023-10-18" @default.
• W1979702960 title "New Homoleptic Organometallic Derivatives of Vanadium(III) and Vanadium(IV): Synthesis, Characterization, and Study of Their Electrochemical Behaviour" @default.
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• W1979702960 doi "https://doi.org/10.1002/chem.200401190" @default.
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