The 1,2-(CH2P(1-adamantyl)2)2C6H4 (dadpx) coordinated palladium complex [(dadpx)Pd(OTf)2] (1) is a catalyst precursor for the isomerizing methoxycarbonylation of the internal double bond of methyl oleate, with an unprecedented selectivity (96%) for the linear diester 1,19-dimethyl nonadecanedioate. Rapid formation of the catalytically active solvent-coordinated hydride species [(dadpx)PdH(MeOH)]+ (3-MeOH) is evidenced by NMR spectroscopy, and further isolation and X-ray crystal structure analysis of [(dadpx)PdH(PPh3)]+ (3-PPh3). DFT calculations of key steps of the catalytic cycle unravel methanolysis as the decisive step for enhanced selectivity and the influence of the rigid adamantyl framework on this step by destabilization of transition states of unselective pathways.
|Original language||English (US)|
|Number of pages||5|
|State||Published - Oct 14 2014|
ASJC Scopus subject areas
- Environmental Chemistry
- Materials Science(all)
- Chemical Engineering(all)
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CCDC 992440: Experimental Crystal Structure Determination : hydrido-((1,2-phenylenebis(methylene))bis(bis(adamantan-1-yl)phosphine))-triphenylphosphine-palladium(ii) trifluoromethanesulfonate methanol solvate
Christl, J. T. (Creator), Roesle, P. (Creator), Stempfle, F. (Creator), Müller, G. (Creator), Caporaso, L. (Creator), Cavallo, L. (Creator), Mecking, S. (Creator), Christl, J. T. (Creator), Roesle, P. (Creator), Stempfle, F. (Creator), Müller, G. (Creator), Caporaso, L. (Creator) & Mecking, S. (Creator), Cambridge Crystallographic Data Centre, Oct 15 2014
DOI: 10.5517/cc129q69, http://hdl.handle.net/10754/624304