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PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
20
pubmed:dateCreated
2004-9-27
pubmed:abstractText
The reactions of 1 or 2 equiv of N-methyl-o-diaminobenzene with trans-[ReOX(3)(PPh(3))(2)] (X = Cl, Br) in refluxing chloroform gave oxo-free rhenium complexes [Re(VI)X(4)(NC(6)H(4)NHCH(3))(OPPh(3))] (X = Cl, 3; X = Br, 6), [Re(V)X(2)Y(NC(6)H(4)NHCH(3))(PPh(3))(2)] (X, Y = Cl, 4; X = Br, Y = Cl, 7), [Re(IV)Cl(2)(NHC(6)H(4)NCH(3))(2)] (5), and [Re(IV)Br(3)(NHC(6)H(4)NCH(3))(PPh(3))] (8). All complexes were characterized by elemental analysis, (1)H NMR and IR spectroscopy, cyclic voltammetry, EPR spectroscopy, and X-ray crystallography. The complexes all display distorted octahedral coordination geometry. For Re(IV) complexes 5 and 8, the ligands coordinate in the benzosemiquinone diimine form. In Re(VI) complexes 3 and 6 and the Re(V) complexes 4 and 7, the ligands coordinate in the dianionic monodentate imido form. The EPR spectra of Re(VI) species 3 and 6 in dichloromethane solution at room temperature exhibit the characteristic hyperfine pattern of six lines, with evidence of strong second-order effects. The IR spectra of the complexes are characterized by Re=N and Re-N stretching bands at ca. 1090 and 540 cm(-)(1), respectively. The Re(IV) and Re(V) complexes display well-resolved NMR spectra, while the Re(VI) complexes exhibit no observable spectra, due to paramagnetism. The cyclic voltammograms of complexes 3 and 6 display Re(VII)/ Re(VI) and Re(VI)/Re(V) processes, those of 4 and 7 exhibit Re(VI)/Re(V) and Re(V)/Re(IV) couples, and those of 5 and 8 are characterized by Re(V)/Re(IV) and Re(IV)/Re(III) processes.
pubmed:language
eng
pubmed:journal
pubmed:citationSubset
IM
pubmed:chemical
pubmed:status
MEDLINE
pubmed:month
Oct
pubmed:issn
0020-1669
pubmed:author
pubmed:issnType
Print
pubmed:day
4
pubmed:volume
43
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
6445-54
pubmed:dateRevised
2006-11-15
pubmed:meshHeading
pubmed:year
2004
pubmed:articleTitle
Unusual reactivity of the [Re(V)O]3+ core: syntheses and characterization of novel rhenium halide complexes with n-methyl-o-diaminobenzene.
pubmed:affiliation
Department of Chemistry, Syracuse University, Syracuse, New York 13244, USA.
pubmed:publicationType
Journal Article, Research Support, U.S. Gov't, Non-P.H.S.