Synthesis and reactivity of palladium hydrido-solvento complexes, including a key intermediate in the catalytic methoxycarbonylation of ethene to methyl propanoate
Abstract
The sequence of reaction steps and the role of each reactant, required for the transformation of the Pd(0) precursor [Pd(dtbpx)(dba)] [dtbpx = 1,2-(CH2PBut2)2C6H4; dba = trans,trans-(PhCHCH)2CO], 1, into [Pd(dtbpx)H(MeOH)]+, 2a, the active Pd(II)-hydride catalyst for the methoxycarbonylation of ethene to methylpropanoate, have been delineated using a combination of spectroscopic and crystallographic methods. The preparation and characterisation of a variety of related complexes are described including some unusual examples involving bidentate sulfonate complexes and mono-cationic and neutral palladium hydride complexes. X-Ray crystal structures have been determined for [Pd(dtbpx)(η2-O2)], 3, [Pd(dtbpx)(η2-BQ)] (BQ = benzoquinone), 4, [Pd(dcpx)(dbaH)]+ [dcpx = 1,2-(CH2PCy2)2C6H4], 7, and [Pd(dtbpx)(η2-MeSO3)]+, 9b.