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]

R. Angharad Baber, Matthew L. Clarke*, A. Guy Orpen, David A. Ratcliffe

*Corresponding author for this work

Research output: Contribution to journalArticle (Academic Journal)peer-review

32 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 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 contributionSynthesis 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]
Original languageEnglish
Pages (from-to)112-119
Number of pages8
JournalJournal of Organometallic Chemistry
Volume667
Issue number1-2
DOIs
Publication statusPublished - 3 Feb 2003

Bibliographical note

Other: Ratcliffe,DA was an undergraduate

Keywords

  • Co-ordination chemistry
  • Hydroformylation
  • Phosphines
  • Rhodium complexes

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