Synthesis and transition metal chemistry of phosphomide ligands

Matthew Lee Clarke, AG Orpen, DA Ratcliffe

Research output: Contribution to journalArticlepeer-review

29 Citations (Scopus)

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 sigma-donor ligands than P-acetyl-diphenylphosphine as determined by the measurement of v(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 pi-acceptor ligand. The crystal structure of [(RhCpCl2)-Cl-*{Ph2PC(O)CH3}] showed a normal pseudo-octahedral piano-stool molecular geometry with a Rh-P bond length of 2.3186(5) Angstrom. 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. (C) 2002 Elsevier Science B.V. All rights reserved.

Original languageEnglish
Pages (from-to)112
Number of pages112
JournalJournal of Organometallic Chemistry
Volume667
Publication statusPublished - 3 Feb 2003

Keywords

  • co-ordination chemistry
  • hydroformylation
  • phosphines
  • rhodium complexes
  • RHODIUM-CATALYZED HYDROFORMYLATION
  • COMPLEXES
  • OLEFINS

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