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}
Φόρτωση...
Ημερομηνία
Συγγραφείς
Triantafillou, G. D.
Tolis, E. I.
Terzis, A.
Deligiannakis, Y.
Raptopoulou, C. P.
Sigalas, M. P.
Kabanos, T. A.
Τίτλος Εφημερίδας
Περιοδικό ISSN
Τίτλος τόμου
Εκδότης
American Chemical Society
Περίληψη
Τύπος
Είδος δημοσίευσης σε συνέδριο
Είδος περιοδικού
peer reviewed
Είδος εκπαιδευτικού υλικού
Όνομα συνεδρίου
Όνομα περιοδικού
Inorg Chem
Όνομα βιβλίου
Σειρά βιβλίου
Έκδοση βιβλίου
Συμπληρωματικός/δευτερεύων τίτλος
Περιγραφή
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-).
Περιγραφή
Λέξεις-κλειδιά
electron-spin-echo, envelope modulation spectroscopy, effective core potentials, metal-binding, vanadium bromoperoxidase, paramagnetic-resonance, ray-structure, active-site, structural-characterization, molecular calculations
Θεματική κατηγορία
Παραπομπή
Σύνδεσμος
<Go to ISI>://000187971500012
http://pubs.acs.org/doi/pdfplus/10.1021/ic034440d
http://pubs.acs.org/doi/pdfplus/10.1021/ic034440d
Γλώσσα
en
Εκδίδον τμήμα/τομέας
Όνομα επιβλέποντος
Εξεταστική επιτροπή
Γενική Περιγραφή / Σχόλια
Ίδρυμα και Σχολή/Τμήμα του υποβάλλοντος
Πανεπιστήμιο Ιωαννίνων. Σχολή Θετικών Επιστημών. Τμήμα Χημείας