Statements in which the resource exists as a subject.
PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
21
pubmed:dateCreated
2002-10-14
pubmed:abstractText
The reaction of (R(2)PCH(2)SiMe(2))(2)NM (PNP(R)M; R = Cy; M = Li, Na, MgHal, Ag) with L(2)ReOX(3) [L(2) = (Ph(3)P)(2) or (Ph(3)PO)(Me(2)S); X = Cl, Br] gives (PNP(Cy))ReOX(2) as two isomers, mer,trans and mer,cis. These compounds undergo a double Si migration from N to O at 90 degrees C to form (POP(Cy))ReNX(2) as a mixture of mer,trans and fac,cis isomers. Additional thermolysis effects migration of CH(3) from Si to Re, along with compensating migration of halide from Re to Si. DFT calculations on various structural isomers support the greater thermodynamic stability of the POP/ReN isomer vs PNP/ReO and highlight the influence of the template effect on the reactivities of these species.
pubmed:language
eng
pubmed:journal
pubmed:status
PubMed-not-MEDLINE
pubmed:month
Oct
pubmed:issn
0020-1669
pubmed:author
pubmed:issnType
Print
pubmed:day
21
pubmed:volume
41
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
5615-25
pubmed:dateRevised
2003-11-3
pubmed:year
2002
pubmed:articleTitle
Double silyl migration converting ORe[N(SiMe(2)CH(2)PCy(2))(2)] to NRe[O(SiMe(2)CH(2)PCy(2))(2)] substructures.
pubmed:affiliation
Department of Chemistry and Molecular Structure Center, Indiana University, Bloomington, IN 47405, USA.
pubmed:publicationType
Journal Article