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11456964

Source:http://linkedlifedata.com/resource/pubmed/id/11456964

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pubmed-article:11456964rdf:typepubmed:Citationlld:pubmed
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pubmed-article:11456964pubmed:issue12lld:pubmed
pubmed-article:11456964pubmed:dateCreated2001-7-17lld:pubmed
pubmed-article:11456964pubmed:abstractTextA single-crystal X-ray determination of the [Li(CH(3)CN)(2)(+)](6-CH(3)-nido-5,6,9-C(3)B(7)H(9)(-)) salt has shown that the 6-CH(3)-nido-5,6,9-C(3)B(7)H(9)(-) tricarbadecaboranyl anion has a nido-cage geometry based on an octadecahedron missing the unique six-coordinate vertex. The resulting six-membered open face is puckered, with two of the cage carbons (C6 and C9) occupying the low-coordinate cage positions above the plane of the four remaining atoms (C5, B7, B8, and B10). The Li(+) ion is centered over the open face and is solvated by two acetonitrile molecules. The reactions of the 6-CH(3)-nido-5,6,9-C(3)B(7)H(9)(-) anion with various vanadium halide salts, including VCl(4), VCl(3), and VBr(2), each resulted in the isolation of the same five paramagnetic products (2-6) of composition V(CH(3)-C(3)B(7)H(9))(2). X-ray crystallographic determinations of 2-5 showed that the complexes consist of two octadecahedral VC(3)B(7) fragments sharing a common vanadium vertex and established their structures as commo-V-(1-V-4'-CH(3)-2',3',4'-C(3)B(7)H(9))(1-V-2-CH(3)-2,3,4-C(3)B(7)H(9)) (2), commo-V-(1-V-5'-CH(3)-2',3',5'-C(3)B(7)H(9))(1-V-4-CH(3)-2,3,4-C(3)B(7)H(9)) (3), commo-V-(1-V-5'-CH(3)-2',3',5'-C(3)B(7)H(9))(1-V-2-CH(3)-2,3,4-C(3)B(7)H(9)) (4), and commo-V-(1-V-2-CH(3)-2,3,4-C(3)B(7)H(9))(2) (5). These complexes can be considered as tricarbadecaboranyl analogues of vanadocene, (eta(5)-C(5)H(5))(2)V. However, unlike vanadocene, these complexes are air- and moisture-stable and have only one unpaired electron. The five complexes differ with respect to one another in that they either (1) contain different enantiomeric forms of the CH(3)-C(3)B(7)H(9) cages, (2) have a different twist orientation of the two cages, or (3) have the methyl group of the CH(3)-C(3)B(7)H(9) cage located in either the 2 or 4 position of the cage. Subsequent attempts to oxidize the compounds with reagents such as Br(2) and Ag(+) were unsuccessful, illustrating the ability of the tricarbadecaboranyl anion to stabilize metals in low oxidation states. Consistent with this, both the electrochemical oxidation and the reduction of 2 were much more positive than those of the same oxidation state changes in vanadocene. The one-electron reduction of 2 is a remarkable 2.9 V positive of that of Cp(2)V.lld:pubmed
pubmed-article:11456964pubmed:languageenglld:pubmed
pubmed-article:11456964pubmed:journalhttp://linkedlifedata.com/r...lld:pubmed
pubmed-article:11456964pubmed:statusPubMed-not-MEDLINElld:pubmed
pubmed-article:11456964pubmed:monthMarlld:pubmed
pubmed-article:11456964pubmed:issn0002-7863lld:pubmed
pubmed-article:11456964pubmed:authorpubmed-author:GarsUUlld:pubmed
pubmed-article:11456964pubmed:authorpubmed-author:WangYYlld:pubmed
pubmed-article:11456964pubmed:authorpubmed-author:KangS OSOlld:pubmed
pubmed-article:11456964pubmed:authorpubmed-author:CarrollP JPJlld:pubmed
pubmed-article:11456964pubmed:authorpubmed-author:WasczcakM DMDlld:pubmed
pubmed-article:11456964pubmed:authorpubmed-author:SneddonL GLGlld:pubmed
pubmed-article:11456964pubmed:authorpubmed-author:GeigerW EWElld:pubmed
pubmed-article:11456964pubmed:issnTypePrintlld:pubmed
pubmed-article:11456964pubmed:day28lld:pubmed
pubmed-article:11456964pubmed:volume123lld:pubmed
pubmed-article:11456964pubmed:ownerNLMlld:pubmed
pubmed-article:11456964pubmed:authorsCompleteYlld:pubmed
pubmed-article:11456964pubmed:pagination2783-90lld:pubmed
pubmed-article:11456964pubmed:dateRevised2003-10-31lld:pubmed
pubmed-article:11456964pubmed:year2001lld:pubmed
pubmed-article:11456964pubmed:articleTitleSyntheses and structural and electrochemical characterizations of vanadatricarbadecaboranyl analogues of vanadocene and the structural characterization of the [Li(CH(3)CN)2+](6-CH(3)-nido-5,6,9-C(3)B(7)H(9-) tricarbadecaboranyl anion.lld:pubmed
pubmed-article:11456964pubmed:affiliationDepartment of Chemistry, University of Pennsylvania, Philadelphia, PA 19104-6323, USA.lld:pubmed
pubmed-article:11456964pubmed:publicationTypeJournal Articlelld:pubmed