Synthesis and transition metal chemistry of 'phosphomide' ligands: A comparison of the reactivity and electronic properties of diphenyl-P-perfluoro-octanoyl-phosphine, P-acetyl-dyphenylphophine and P-anisoyl-diphenylphosphine. X-ray crystal structure of [RhCp*(Ph2PC(O)CH3)Cl2]
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-acetyldiphenylphosphine as determined by the measurement of ν(CO) for the corresponding rhodium carbonyl complexes trans - [RhL2(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*Cl2{Ph2PC(O)CH3}] showed a normal pseudo-octahedral pianostool molecular geometry with a Rh-P bond length of 2.3186(5) A?. 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.
Baber, R. Angharad,Clarke, Matthew L.,Orpen, A. Guy,Ratcliffe, David A.
p. 112 - 119
(2007/10/03)
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