Synthesis of novel terminal iridium phosphinidene complexes

Arjan T. Termaten, Tom Nijbacker, Marius Schakel, Martin Lutz, Anthony L. Spek, Koop Lammertsma

Research output: Contribution to journalArticlepeer-review

64 Citations (Scopus)

Abstract

Stable, crystalline iridium-complexed phosphinidenes, Cp*(L)Ir=PR, are readily synthesized by (a) the reaction of Cp*(L)IrCl2 (2, L = PPh3) with LiPHMes* and (b) dehydrohalogenation of Cp*(PH2R)IrCl2 (5, R = Mes*, Is, Mes) with in situ capturing of transient Cp*Ir≢PR (4) with phosphines, phosphites, arsines, isocyanides, and carbon monoxide (L). Cp*Ir≢PR eluded direct detection. The X-ray crystal structures are reported for Cp*(PPh3)Ir=PMes* (3) and Cp*(CO)Ir=PMes* (15). The more congested 3 has an E configuration for its Ir=P bond, whereas 15 is obtained in its Z form. The 31P NMR chemical shifts and 2Jpp coupling constants are diagnostic for the E and Z forms. More shielded phosphinidene resonances and larger coupling constants are typical for the E isomers. These iridium-complexed phosphinidenes react with gem-diiodides to form phosphaalkenes, but not with carbonyl groups.

Original languageEnglish
Pages (from-to)3196-3202
Number of pages7
JournalOrganometallics
Volume21
Issue number15
DOIs
Publication statusPublished - 22 Jul 2002
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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