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}

Triantafillou, G. D.; Tolis, E. I.; Terzis, A.; Deligiannakis, Y.; Raptopoulou, C. P.; Sigalas, M. P.; Kabanos, T. A.

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}

dc.contributor.author	Triantafillou, G. D.	en
dc.contributor.author	Tolis, E. I.	en
dc.contributor.author	Terzis, A.	en
dc.contributor.author	Deligiannakis, Y.	en
dc.contributor.author	Raptopoulou, C. P.	en
dc.contributor.author	Sigalas, M. P.	en
dc.contributor.author	Kabanos, T. A.	en
dc.date.accessioned	2015-11-24T16:42:16Z
dc.date.available	2015-11-24T16:42:16Z
dc.identifier.issn	0020-1669	-
dc.identifier.uri	https://olympias.lib.uoi.gr/jspui/handle/123456789/8528
dc.rights	Default Licence	-
dc.subject	electron-spin-echo	en
dc.subject	envelope modulation spectroscopy	en
dc.subject	effective core potentials	en
dc.subject	metal-binding	en
dc.subject	vanadium bromoperoxidase	en
dc.subject	paramagnetic-resonance	en
dc.subject	ray-structure	en
dc.subject	active-site	en
dc.subject	structural-characterization	en
dc.subject	molecular calculations	en
dc.title	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
heal.abstract	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
heal.access	campus	-
heal.fullTextAvailability	TRUE	-
heal.identifier.primary	Doi 10.1021/Ic034440d	-
heal.identifier.secondary	<Go to ISI>://000187971500012	-
heal.identifier.secondary	http://pubs.acs.org/doi/pdfplus/10.1021/ic034440d	-
heal.journalName	Inorg Chem	en
heal.journalType	peer reviewed	-
heal.language	en	-
heal.publicationDate	2004	-
heal.publisher	American Chemical Society	en
heal.recordProvider	Πανεπιστήμιο Ιωαννίνων. Σχολή Θετικών Επιστημών. Τμήμα Χημείας	el
heal.type	journalArticle	-
heal.type.el	Άρθρο Περιοδικού	el
heal.type.en	Journal article	en

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