Monomeric oxovanadium(IV) compounds of the general formula cis-[V-IV(=O)(X)(L-NN)2](+/0) {X = OH-, Cl-, SO42- and L-NN = 2,2 '-Bipyridine (Bipy) or 4,4 '-disubstituted bipy}

 
This item is provided by the institution :
University of Ioannina
Repository :
Repository of UOI Olympias
see the original item page
in the repository's web site and access all digital files if the item*
share



2004 (EN)
Monomeric oxovanadium(IV) compounds of the general formula cis-[V-IV(=O)(X)(L-NN)2](+/0) {X = OH-, Cl-, SO42- and L-NN = 2,2 '-Bipyridine (Bipy) or 4,4 '-disubstituted bipy} (EN)

Triantafillou, G. D. (EN)

Πανεπιστήμιο Ιωαννίνων. Σχολή Θετικών Επιστημών. Τμήμα Χημείας (EL)
Triantafillou, G. D. (EN)

Reaction of [(VOCl2)-O-IV(THF)(2)] in aqueous solution with 2 equiv of AgBF4 or AgSbF6 and then with 2 equiv of 2,2'-bipyridine (bipy), 4,4'-di-tert-butyl-2,2'-bipyridine (4,4'-dtbipy), or 4,4'-di-methyl-2,2'-bipyridine (4,4'-dmbipy) affords compounds of the general formula cis-[(VO)-O-IV(OH)(L-NN)(2)]Y {where L-NN = bipy, Y = BF4(-) (1), L-NN = 4,4'-dtbipy, Y = BF4(-) (2.1.2H(2)O), L-NN = 4,4'-dmbipy, Y = BF4(-) (3.2H(2)O), and L-NN = 4,4'-dtbipy, Y = SbF6- (4)}. Sequential addition of 1 equiv of Ba(ClO4)(2) and then of 2 equiv of bipy to an aqueous solution containing 1 equiv of (VOSO4)-O-IV.5H(2)O yields cis-[(VO)-O-IV(OH)(bipy)(2)]ClO4 (5). The monomeric compounds 1-5 contain the cis-[(VO)-O-IV(OH)](+) structural unit. Reaction of 1 equiv Of (VOSO4)-O-IV.5H(2)O in water and of 1 equiv Of [(VOCl2)-O-IV(THF)(2)] in ethanol with 2 equiv of bipy gives the compounds cis-[(VO)-O-IV(OSO3)(bipy)(2)].CH3OH.1.5H(2)O (6.CH3OH.1.5H(2)O) and cis-[(VOCl)-O-IV(bipy)(2)]Cl (7), respectively, while reaction of 1 equiv of [(VOCl2)-O-IV(THF)(2)] in CH2Cl2 with 2 equiv of 4,4'-dtbipy gives the compound cis-[(VOCl)-O-IV(4,4'-dtbipy)(2)]Cl.0.5CH(2)Cl(2) (8.0.5CH(2)Cl(2)). Compounds cis-[(VO)-O-IV(BF4)(4,4'-dtbipy)(2)]BF4 (9), cis-[(VO)-O-IV(BF4)(4,4'-dmbipy)(2)]BF4 (10), and cis-[(VO)-O-IV(SbF6)(4,4'-dtbipy)(2)]SbF6 (11) were synthesized by sequential addition of 2 equiv of 4,4'-dtbipy or 4,4'-dmbipy and 2 equiv of AgBF4 or AgSbF6 to a dichloromethane solution containing 1 equiv of [(VOCl2)-O-IV(THF)(2)]. The crystal structures of 2.1.2H(2)O, 6.CH3OH.1.5H(2)O, and 8.0.5CH(2)Cl(2) were demonstrated by X-ray diffraction analysis. Crystal data are as follows: Compound 2.1.2H(2)O crystallizes in the orthorhombic space group Pbca with (at 298 K) a = 21.62(1) Angstrom, b = 13.33(1) Angstrom, c = 27.25(2) Angstrom, V = 7851(2) Angstrom(3), Z = 8. Compound 6.CH3OH.1.5H(2)O crystallizes in the monoclinic space group P2(1)/a with (at 298 K) a = 12.581(4) Angstrom, b = 14.204(5) Angstrom, c = 14.613(6) Angstrom, beta = 11 4.88(1)degrees, V = 2369(1), Z = 4. Compound 8.0.5CH(2)Cl(2) crystallizes in the orthorhombic space group Pca2(1) with (at 298 K) a = 23.072(2) Angstrom, b = 24.176(2) Angstrom, c = 13.676(1) Angstrom, V = 7628(2) Angstrom(3), Z = 8 with two crystallographically independent molecules per asymmetric unit. In addition to the synthesis and crystallographic studies, we report the optical, infrared, magnetic, conductivity, and CW EPR properties of these oxovanadium(IV) compounds as well as theoretical studies on [(VO)-O-IV(bipy)(2)](2+) and [(VOX)-O-IV(bipy)(2)](+/0) species (X = OH-, SO42-, Cl-). (EN)

electron-spin-echo (EN)

Πανεπιστήμιο Ιωαννίνων (EL)
University of Ioannina (EN)

Inorg Chem (EN)

English

2004

<Go to ISI>://000187971500012

American Chemical Society (EN)



*Institutions are responsible for keeping their URLs functional (digital file, item page in repository site)