Linked Life Data

17177409

Source:http://linkedlifedata.com/resource/pubmed/id/17177409

Statements in which the resource exists as a subject.
PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
51
pubmed:dateCreated
2006-12-20
pubmed:abstractText
Treatment of the eta9,eta5-bis(indenyl)zirconium sandwich complex, (eta9-C9H5-1,3-(SiMe3)2)(eta5-C9H5-1,3-(SiMe3)2)Zr, with dialkyl ethers such as diethyl ether, CH3OR (R=Et, nBu, tBu), nBu2O, or iPr2O resulted in facile C-O bond scission furnishing an eta5,eta5-bis(indenyl)zirconium alkoxy hydride complex and free olefin. In cases where ethylene is formed, trapping by the zirconocene sandwich yields a rare example of a crystallographically characterized, base-free eta5,eta5-bis(indenyl)zirconium ethylene complex. Observation of normal, primary kinetic isotope effects in combination with rate studies and the stability of various model compounds support a mechanism involving rate-determining C-H activation to yield an eta5,eta5-bis(indenyl)zirconium alkyl hydride intermediate followed by rapid beta-alkoxide elimination. For isolable eta6,eta5-bis(indenyl)zirconium THF compounds, thermolysis at 85 degrees C also resulted in C-O bond cleavage to yield the corresponding zirconacycle. Both mechanistic and computational studies again support a pathway involving haptotropic rearrangement to eta5,eta5-bis(indenyl)zirconium intermediates that promote rate-determining C-H activation and ultimately C-O bond scission.
pubmed:language
eng
pubmed:journal
pubmed:citationSubset
IM
pubmed:chemical
pubmed:status
MEDLINE
pubmed:month
Dec
pubmed:issn
0002-7863
pubmed:author
pubmed:issnType
Print
pubmed:day
27
pubmed:volume
128
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
16600-12
pubmed:meshHeading
pubmed:year
2006
pubmed:articleTitle
Carbon-oxygen bond cleavage with eta9,eta5-bis(indenyl)zirconium sandwich complexes.
pubmed:affiliation
Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, NY 14853, USA.
pubmed:publicationType
Journal Article, Research Support, Non-U.S. Gov't