Premium
Exploring (Ph 2 PCH 2 CH 2 ) 2 E Ligand Space (E = O, S, PPh) in Rh I Alkene Complexes as Potential Hydroacylation Catalysts
Author(s) -
Pike Sebastian D.,
Pawley Rebekah J.,
Chaplin Adrian B.,
Thompson Amber L.,
Hooper Joel A.,
Willis Michael C.,
Weller Andrew S.
Publication year - 2011
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201100958
Subject(s) - chemistry , hydroacylation , alkene , reactivity (psychology) , substituent , aldehyde , ligand (biochemistry) , methyl acrylate , chelation , medicinal chemistry , nuclear magnetic resonance spectroscopy , stereochemistry , photochemistry , organic chemistry , catalysis , medicine , biochemistry , polymer , alternative medicine , receptor , pathology , copolymer
The ligands (Ph 2 PCH 2 CH 2 ) 2 E (E = O, S, PPh) have been used to form a variety of Rh I cations [Rh{(Ph 2 PCH 2 CH 2 ) 2 E}(alkene)] + (alkene = methyl acrylate, trimethylvinylsilane). Variable‐temperature NMR spectroscopy shows that the methyl acrylate ligands undergo a fluxional process on the metal, via a κ 1 ‐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.