Abstract
A convenient synthesis of several ‘phosphomide’ ligands (P adjacent to carbonyl group) from secondary phosphines is reported. The new anisoyl substituted phosphines are considerable more stable to hydrolysis, and are stronger σ-donor ligands than P-acetyl-diphenylphosphine as determined by the measurement of ν(CO) for the corresponding rhodium carbonyl complexes trans-[RhL 2(CO)Cl]. In contrast, a new phosphomide derived from perfluoro-octanoyl chloride was found to be a highly unstable, electron poor π-acceptor ligand. The crystal structure of [RhCp*Cl 2{Ph 2PC(O)CH 3}] showed a normal pseudo-octahedral piano-stool molecular geometry with a RhP bond length of 2.3186(5) Å. The extra stability observed for the P-anisoyl phosphomides has led us to apply this class of ligand in rhodium catalysed hydroformylation for the first time.
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