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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. 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 |
|---|---|
| Subjects: | Q Science > QD Chemistry |
| Divisions: | Faculty of 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 |
| Date: | December 2011 |
| Volume: | Vol.2011 |
| Number: | No.36 |
| Page Range: | pp. 5558-5565 |
| Identification Number: | 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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| URI: | http://wrap.warwick.ac.uk/id/eprint/40483 |
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