uu.seUppsala universitets publikasjoner
Endre søk
RefereraExporteraLink to record
Permanent link

Direct link
Referera
Referensformat
  • apa
  • ieee
  • modern-language-association
  • vancouver
  • Annet format
Fler format
Språk
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Annet språk
Fler språk
Utmatningsformat
  • html
  • text
  • asciidoc
  • rtf
Quantitative Determination of the Regioselectivity of Nucleophilic Addition to η3-Propargyl Rhenium Complexes and Direct Observation of an Equilibrium between η3-Propargyl Rhenium Complexes and Rhenacyclobutenes.
2009 (engelsk)Inngår i: Organometallics, ISSN 0276-7333, E-ISSN 1520-6041, Vol. 28, nr 1, s. 123-131Artikkel i tidsskrift (Fagfellevurdert) Published
Abstract [en]

PMe3 adds selectively to the central C of the η3-propargyl complex [C5Me5(CO)2Re(η3-CH2C≡CCMe3)][BF4] (1-t-Bu) to form the metallacyclobutene [C5Me5(CO)2Re(CH2C(PMe3):CCMe3)][BF4] (7). The rate of rearrangement of the metallacyclobutene 7 to η2-alkyne complex [C5Me5(CO)2Re(η2-Me3PCH2C≡CCMe3)][BF4] (8) is independent of phosphine concn., consistent with a dissociative mechanism proceeding via η3-propargyl complex 1-t-Bu. The rate of this rearrangement is 480 times slower than the rate of exchange of PMe3 with the labeled metallacyclobutene 7-d9. This rate ratio provides an indirect measurement of the regioselectivity for addn. of PMe3 to the central C of η3-propargyl complex 1-t-Bu to give 7 compared to addn. to a terminal C to give 8. The addn. of PPh3 to 1-t-Bu gives the metallacyclobutene [C5Me5(CO)2Re(CH2C(PPh3):CCMe3)][BF4] (11). Low-temp. 1H NMR spectra provide evidence for an equil. between metallacyclobutene 11 and η3-propargyl complex 1-t-Bu (Keq ≈ 44 M-1 at -46° and ΔG°(0°) = -1.2 ± 0.2 kcal mol-1). The crystal and mol. structures of [C5Me5(CO)2Re[η2-(Ar2PCH2CH2PPh2)CH2C≡CCMe3]][BF4]·2CH2Cl2 (Ar = 3,5-(CF3)2C6H3) and [C5Me5(CO)2Re(η2-Me3PCH2C≡CCMe3)]Cl·H2O were detd. by x-ray crystallog. [on SciFinder(R)]

sted, utgiver, år, opplag, sider
2009. Vol. 28, nr 1, s. 123-131
Emneord [en]
rhenium cyclopentadienyl carbonyl propargyl complex nucleophilic addn phosphine regioselectivity, crystal structure rhenium cyclopentadienyl carbonyl alkynylphosphonioethylphosphine alkynylphosphonium complex, mol structure rhenium cyclopentadienyl carbonyl alkynylphosphonioethylphosphine alkynylphosphonium complex, kinetics phosphine nucleophilic addn rhenium propargyl complex, exchange rearrangement kinetics thermodn phosphoniorhenacyclobutene
HSV kategori
Identifikatorer
URN: urn:nbn:se:uu:diva-174513DOI: 10.1021/om800739jOAI: oai:DiVA.org:uu-174513DiVA, id: diva2:527606
Merknad
CAPLUS AN 2008:1418835(Journal)Tilgjengelig fra: 2012-05-21 Laget: 2012-05-21 Sist oppdatert: 2017-12-07

Open Access i DiVA

Fulltekst mangler i DiVA

Andre lenker

Forlagets fulltekst

Personposter BETA

Samec, Joseph S. M.

Søk i DiVA

Av forfatter/redaktør
Samec, Joseph S. M.
I samme tidsskrift
Organometallics

Søk utenfor DiVA

GoogleGoogle Scholar

doi
urn-nbn

Altmetric

doi
urn-nbn
Totalt: 495 treff
RefereraExporteraLink to record
Permanent link

Direct link
Referera
Referensformat
  • apa
  • ieee
  • modern-language-association
  • vancouver
  • Annet format
Fler format
Språk
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Annet språk
Fler språk
Utmatningsformat
  • html
  • text
  • asciidoc
  • rtf