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

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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
Official Date:	December 2011
Dates:	Date Event December 2011 Published
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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