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Exploring (Ph2PCH2CH2)2E ligand space (E = O, S, PPh) in RhI alkene complexes as potential hydroacylation catalysts
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Pike, Sebastian D., Pawley, R, Chaplin, Adrian B., Thompson, Amber L., Hooper, Joel A., Willis, Michael C. and Weller, Andrew S. (2011) Exploring (Ph2PCH2CH2)2E ligand space (E = O, S, PPh) in RhI alkene complexes as potential hydroacylation catalysts. European Journal of Inorganic Chemistry, Vol.2011 (No.36). pp. 5558-5565. doi:10.1002/ejic.201100958 ISSN 1434-1948.
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Official URL: http://dx.doi.org/10.1002/ejic.201100958
Abstract
The ligands (Ph2PCH2CH2)2E (E = O, S, PPh) have been used to form a variety of RhI cations [Rh{(Ph2PCH2CH2)2E}(alkene)]+ (alkene = methyl acrylate, trimethylvinylsilane). Variable-temperature NMR spectroscopy shows that the methyl acrylate ligands undergo a fluxional process on the metal, via a κ1-carbonyl intermediate, while the trimethylvinylsilane complexes cannot access this intermediate and do not undergo the same process. Their reactivity in hydroacylation reactions with 1-pentanal have been investigated, and these studies further suggest the important role that a chelating substituent next to the aldehyde might play in productive hydroacylation.
Item Type: | Journal Article | ||||
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Subjects: | Q Science > QD Chemistry | ||||
Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | ||||
Library of Congress Subject Headings (LCSH): | Rhodium, Nuclear magnetic resonance spectroscopy, Alkenes, Catalysts, Ligands | ||||
Journal or Publication Title: | European Journal of Inorganic Chemistry | ||||
Publisher: | Wiley-VCH Verlag GMBH | ||||
ISSN: | 1434-1948 | ||||
Official Date: | December 2011 | ||||
Dates: |
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Volume: | Vol.2011 | ||||
Number: | No.36 | ||||
Page Range: | pp. 5558-5565 | ||||
DOI: | 10.1002/ejic.201100958 | ||||
Status: | Peer Reviewed | ||||
Publication Status: | Published | ||||
Access rights to Published version: | Restricted or Subscription Access | ||||
Funder: | Engineering and Physical Sciences Research Council (EPSRC), University of Oxford |
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