Statements in which the resource exists.
SubjectPredicateObjectContext
pubmed-article:18788735rdf:typepubmed:Citationlld:pubmed
pubmed-article:18788735lifeskim:mentionsumls-concept:C0205131lld:lifeskim
pubmed-article:18788735lifeskim:mentionsumls-concept:C0032712lld:lifeskim
pubmed-article:18788735lifeskim:mentionsumls-concept:C1280500lld:lifeskim
pubmed-article:18788735lifeskim:mentionsumls-concept:C0030011lld:lifeskim
pubmed-article:18788735lifeskim:mentionsumls-concept:C0023688lld:lifeskim
pubmed-article:18788735lifeskim:mentionsumls-concept:C2603343lld:lifeskim
pubmed-article:18788735lifeskim:mentionsumls-concept:C1527178lld:lifeskim
pubmed-article:18788735lifeskim:mentionsumls-concept:C0220853lld:lifeskim
pubmed-article:18788735pubmed:issue21lld:pubmed
pubmed-article:18788735pubmed:dateCreated2008-10-28lld:pubmed
pubmed-article:18788735pubmed:abstractTextOxyl radical character in the MnO group of the title system is shown from a density functional theory study to be essential for efficient C-H cleavage, which is a key step in C-H oxidation. Since oxyl species have elongated Mn-O bonds relative to the more usual oxo species of type MnO, the normal expectation would be that high trans-influence ligands X should facilitate oxyl character by elongating the Mn-O bond and thus enhance both oxyl character and reactivity. Contrary to this expectation, but in line with the experimental data (Jin, N.; Ibrahim, M.; Spiro, T. G.; Groves, J. T. J. Am. Chem. Soc. 2007, 129, 12416), we find that reactivity increases along the series X = O(2-) < OH(-) < H2O for the following reasons. The ground-state singlet (S) is unreactive for all X, and only the higher-energy triplet (T) and quintet (Q) states have the oxyl character needed for reactivity, but the higher trans-influence X ligands are also shown to increase the S/T and S/Q gaps, thus making attainment of the needed T and Q states harder. The latter effect is dominant, and high trans-influence X ligands thus disfavor reaction. The higher reactivity in the presence of acid noted by Groves and co-workers is thus rationalized by the preference for having X = H2O over OH(-) or O(2-).lld:pubmed
pubmed-article:18788735pubmed:languageenglld:pubmed
pubmed-article:18788735pubmed:journalhttp://linkedlifedata.com/r...lld:pubmed
pubmed-article:18788735pubmed:citationSubsetIMlld:pubmed
pubmed-article:18788735pubmed:chemicalhttp://linkedlifedata.com/r...lld:pubmed
pubmed-article:18788735pubmed:chemicalhttp://linkedlifedata.com/r...lld:pubmed
pubmed-article:18788735pubmed:chemicalhttp://linkedlifedata.com/r...lld:pubmed
pubmed-article:18788735pubmed:chemicalhttp://linkedlifedata.com/r...lld:pubmed
pubmed-article:18788735pubmed:chemicalhttp://linkedlifedata.com/r...lld:pubmed
pubmed-article:18788735pubmed:chemicalhttp://linkedlifedata.com/r...lld:pubmed
pubmed-article:18788735pubmed:chemicalhttp://linkedlifedata.com/r...lld:pubmed
pubmed-article:18788735pubmed:chemicalhttp://linkedlifedata.com/r...lld:pubmed
pubmed-article:18788735pubmed:chemicalhttp://linkedlifedata.com/r...lld:pubmed
pubmed-article:18788735pubmed:statusMEDLINElld:pubmed
pubmed-article:18788735pubmed:monthNovlld:pubmed
pubmed-article:18788735pubmed:issn1520-510Xlld:pubmed
pubmed-article:18788735pubmed:authorpubmed-author:CrabtreeRober...lld:pubmed
pubmed-article:18788735pubmed:authorpubmed-author:EisensteinOdi...lld:pubmed
pubmed-article:18788735pubmed:authorpubmed-author:BalcellsDavid...lld:pubmed
pubmed-article:18788735pubmed:authorpubmed-author:RaynaudChrist...lld:pubmed
pubmed-article:18788735pubmed:issnTypeElectroniclld:pubmed
pubmed-article:18788735pubmed:day3lld:pubmed
pubmed-article:18788735pubmed:volume47lld:pubmed
pubmed-article:18788735pubmed:ownerNLMlld:pubmed
pubmed-article:18788735pubmed:authorsCompleteYlld:pubmed
pubmed-article:18788735pubmed:pagination10090-9lld:pubmed
pubmed-article:18788735pubmed:meshHeadingpubmed-meshheading:18788735...lld:pubmed
pubmed-article:18788735pubmed:meshHeadingpubmed-meshheading:18788735...lld:pubmed
pubmed-article:18788735pubmed:meshHeadingpubmed-meshheading:18788735...lld:pubmed
pubmed-article:18788735pubmed:meshHeadingpubmed-meshheading:18788735...lld:pubmed
pubmed-article:18788735pubmed:meshHeadingpubmed-meshheading:18788735...lld:pubmed
pubmed-article:18788735pubmed:meshHeadingpubmed-meshheading:18788735...lld:pubmed
pubmed-article:18788735pubmed:meshHeadingpubmed-meshheading:18788735...lld:pubmed
pubmed-article:18788735pubmed:meshHeadingpubmed-meshheading:18788735...lld:pubmed
pubmed-article:18788735pubmed:meshHeadingpubmed-meshheading:18788735...lld:pubmed
pubmed-article:18788735pubmed:meshHeadingpubmed-meshheading:18788735...lld:pubmed
pubmed-article:18788735pubmed:year2008lld:pubmed
pubmed-article:18788735pubmed:articleTitleA rational basis for the axial ligand effect in C-H oxidation by [MnO(porphyrin)(X)]+ (X = H2O, OH-, O2-) from a DFT study.lld:pubmed
pubmed-article:18788735pubmed:affiliationInstitut Charles Gerhardt Montpellier, UMR 5253 CNRS-UM2-ENSCM-UM1, Universite Montpellier 2, cc-1501 Place Eugene Bataillon, 34095, Montpellier, France.lld:pubmed
pubmed-article:18788735pubmed:publicationTypeJournal Articlelld:pubmed
http://linkedlifedata.com/r...pubmed:referesTopubmed-article:18788735lld:pubmed
http://linkedlifedata.com/r...pubmed:referesTopubmed-article:18788735lld:pubmed
http://linkedlifedata.com/r...pubmed:referesTopubmed-article:18788735lld:pubmed
http://linkedlifedata.com/r...pubmed:referesTopubmed-article:18788735lld:pubmed