Unexpected Synthesis of an Unsymmetrical mu-Oxido Divanadium(V) Compound through a Reductive Cleavage of a N-O Bond and Cleavage-Hydrolysis of a C-N Bond of an N,N-Disubstituted Bis-(hydroxylamino) Ligand
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Ημερομηνία
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 the N,N-disubstituted bis-(hydroxylamino) ligand 2,6-bis [hydroxy(methyl)amino]-4-morpholino-1,3,5-triazine, H(2)bihyat, with V(IV)OSO(4)center dot 5H(2)O in water for 6 h followed by the addition of methyl alcohol resulted in the isolation of the unsymmetrical mu-oxido divanadium(V) compound [V(2)(V)O(2)(mu(2)-O)(bihyat)(hyta)(hyto)]center dot 3H(2)O (1 center dot 3H(2)O) and of the methylhydroxylamido derivative [V(V)O(bihyat)(CH(3)NHO)]center dot H(2)O (2 center dot H(2)O). The N,N-disubstituted mono(hydroxylamino) ligands Hhyta, Hhyto, and CH(3)NHOH were formed by the decomposition of the ligand H(2)bihyat in the presence of vanadium. The structures of compounds 1 center dot 3H(2)O and 2 center dot H(2)O were determined by X-ray crystallography. The structure of 1 center dot 3H(2)O consists of one five-coordinate vanadium(V) atom and one six-coordinate vanadium(V) atom bridged by an oxido group and ligated to a tridentate bihyat(2-) and two bidentate hyta(-) and hyto(-) ligands, respectively. The two terminal oxido groups in 1 center dot 3H(2)O are syn-directed, lying on the same side of the V-O-V plane. The coordination environment of the vanadium atom in 2 center dot H(2)O approximates to a highly distorted pentagonal pyramid with the oxido ligand occupying the apical position. Compounds 1 center dot 3H(2)O and 2 center dot H(2)O were studied by multinuclear NMR ((1)H, (13)C, and (51)V) to elucidate their solution structures. The (51)V NMR of 1 center dot 3H(2)O in anhydrous CD(2)Cl(2) gave two signals at -199 and -508 ppm, which were assigned to the five- and six-coordinate vanadium(V) atoms, respectively. The resonance of the five-coordinate vanadium nucleus, in a field much lower than that expected from Rehder's [Inorg. Chem., 1988, 27, 584-587] referencing scale, was attributed to the low-energy ligand-to-metal charge transfer transition at 605 nm [epsilon(M)=5050 M(-1) cm(-1)] of 1 center dot 3H(2)O according to Pecoraro et al. [J. Am. Chem. Soc., 1992, 114, 9925-9933], Electrospray ionization-mass spectrometry studies were used to follow the decomposition products of H(2)bihyat in the presence of vanadium.
Περιγραφή
Λέξεις-κλειδιά
vanadium-dependent haloperoxidases, density-functional theory, solid-state, electron-transfer, v-51 nmr, spectroscopic characterization, structural-characterization, pot conversion, active-site, acetic-acid
Θεματική κατηγορία
Παραπομπή
Σύνδεσμος
<Go to ISI>://000272935800009
http://pubs.acs.org/doi/pdfplus/10.1021/ic901809f
http://pubs.acs.org/doi/pdfplus/10.1021/ic901809f
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