Linked Life Data

17243835

Source:http://linkedlifedata.com/resource/pubmed/id/17243835

Statements in which the resource exists as a subject.
PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
4
pubmed:dateCreated
2007-1-24
pubmed:abstractText
Upon treatment with [PdCl(allyl)]2, asymmetrically substituted alpha,alpha'-diphosphanyl diazo compounds eliminate dinitrogen to afford C-chlorodiphosphanylmethanide complexes in high yields. In the presence of a chloride-abstracting agent, such as sodium tetraphenylborate, the C-chlorodiphosphanylmethanide complexes react with pyridine and trimethylphosphine, readily affording the corresponding nitrogen and phosphorus ylides. The postulated intermediate in this process, namely palladadiphosphanylcarbenes, could not be spectroscopically characterized, but their transient formation was chemically supported further by a Lewis base exchange reaction between pyridine and 4-dimethylaminopyridine. This hypothesis has also been substantiated by computing the corresponding dissociation energy using two model systems featuring methyl groups at the phosphorus. Of particular interest, density functional theory calculations reveal that these palladadiphosphanylcarbenes have a singlet ground state with an "inverse" ppi2 electronic configuration and a distorted geometry associated with unusual transannular metal-carbene interactions (piC-->Pd donation and sigmaPd-->C back-donation).
pubmed:grant
pubmed:commentsCorrections
pubmed:language
eng
pubmed:journal
pubmed:citationSubset
IM
pubmed:chemical
pubmed:status
MEDLINE
pubmed:month
Jan
pubmed:issn
0002-7863
pubmed:author
pubmed:issnType
Print
pubmed:day
31
pubmed:volume
129
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
978-85
pubmed:dateRevised
2011-6-15
pubmed:meshHeading
pubmed:year
2007
pubmed:articleTitle
Transient palladadiphosphanylcarbenes: singlet carbenes with an "inverse" electronic configuration (p(pi)2 instead of sigma2) and unusual transannular metal-carbene interactions (piC-->Pd donation and sigmaPd-->C back-donation).
pubmed:affiliation
Laboratoire Hétérochimie Fondamentale et Appliquée du CNRS (UMR 5069), Université Paul Sabatier, 118, route de Narbonne, F-31062 Toulouse Cedex 9, France.
pubmed:publicationType
Journal Article, Research Support, Non-U.S. Gov't, Research Support, N.I.H., Extramural