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-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) 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. © 2002 Elsevier Science B.V. All rights reserved.
Translated title of the contribution | Synthesis and transition metal chemistry of 'phosphomide' ligands: a comparision of the reactivity and electronic properties of diphenyl-P-perfluoro-octanoyl-phosphine, P-acetyl-diphenylphosphine and P-anisoyl-diphenylphosphine. X-ray crystal structure of [RhCp*(Ph2PC(O)CH3)Cl2] |
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Original language | English |
Pages (from-to) | 112-119 |
Number of pages | 8 |
Journal | Journal of Organometallic Chemistry |
Volume | 667 |
Issue number | 1-2 |
DOIs | |
Publication status | Published - 3 Feb 2003 |
Bibliographical note
Other: Ratcliffe,DA was an undergraduateKeywords
- Co-ordination chemistry
- Hydroformylation
- Phosphines
- Rhodium complexes