Linked Life Data

17967019

Source:http://linkedlifedata.com/resource/pubmed/id/17967019

Statements in which the resource exists as a subject.
PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
46
pubmed:dateCreated
2007-11-16
pubmed:abstractText
Reaction of d0 Ta(NMe2)5 (1) with O2 yields two aminoxy complexes (Me2N)(n)Ta(eta2-ONMe2)(5-n) (n = 4, 2; 3, 3) as well as (Me2N)4Ta2[eta2-N(Me)CH2NMe2]2(mu-O)2 (4) and (Me2N)6Ta3[eta2-N(Me)CH2NMe2]2(eta2-ONMe2)(mu-O)3 (5) containing novel chelating (aminomethyl)amide-N(Me)CH2NMe2 ligands. The crystal structures of 2-5 have been determined by X-ray crystallography. (Me2N)4Ta(eta2-ONMe2) (2) converts to (Me2N)3Ta(eta2-ONMe2)2 (3) in its reaction with O2. In addition, the reaction of Ta(NMe2)5 with 3 gives 2 only at elevated temperatures. Density functional theory (DFT) calculations have been used to investigate the mechanistic pathways in the reactions of Ta(NMe2)5 (1) with triplet O2. Monomeric reaction pathways in the formation of 2-5 are proposed. A key step is the oxygen insertion into a Ta-N bond in 1 through an intersystem conversion from triplet to singlet energy surface to give an active peroxide complex (Me2N)4Ta(eta2-O-O-NMe2) (A4). The DFT studies indicate that the peroxide ligand plays an important role, including oxidizing an amide to an imine ligand through the abstraction of a hydride. Insertion of Me-N=CH2 into a Ta-amide bond yields the unusual -N(Me)CH2NMe2 ligands.
pubmed:language
eng
pubmed:journal
pubmed:citationSubset
IM
pubmed:chemical
pubmed:status
MEDLINE
pubmed:month
Nov
pubmed:issn
0002-7863
pubmed:author
pubmed:issnType
Print
pubmed:day
21
pubmed:volume
129
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
14408-21
pubmed:meshHeading
pubmed:year
2007
pubmed:articleTitle
Reaction of Ta(NMe2)5 with O2: formation of aminoxy and unusual (aminomethyl)amide oxo complexes and theoretical studies of the mechanistic pathways.
pubmed:affiliation
Department of Chemistry, University of Tennessee, Knoxville, Tennessee 37996, USA.
pubmed:publicationType
Journal Article, Research Support, U.S. Gov't, Non-P.H.S., Research Support, Non-U.S. Gov't