Ligand additions to Cp*(CO)2Re=Re(CO)2Cp* and fragmentation and rearrangement reactions of Cp*(CO)2Re(μ-CO)Re(CO)(L)Cp*

Charles P. Casey, Ronald S. Cariño, Hiroyuki Sakaba, Randy K. Hayashi

Research output: Contribution to journalArticle

19 Citations (Scopus)

Abstract

Reaction of Cp*(CO)2Re=Re(CO)2Cp* (1) with CO produced the stable adduct Cp*(CO)2Re-(μ-CO)Re(CO)2Cp* (2). Reaction of 1 with CH3CN gave the stable adduct Cp*(CO)2Re(μ-CO)Re(CO)(CH3CN)Cp* (6). Reaction of 1 with PMe3 or CH2=CH2 at low temperature produced the adducts Cp*(CO)2Re(μ-CO)Re(CO)(PMe3)Cp* (5) and Cp*(CO)2Re(μ-CO)Re-(CO)(CH2=CH 2)Cp* (7), which fragment at -20°C to Cp*Re(CO)2(THF) and either Cp*Re-(CO)2(PMe3) or Cp*Re(CO)2(CH2=CH2). Reaction of 1 with HC=CH gave the dimetallacyclopentenone Cp*(CO)2Re(μ-η13-CH=CHCO)Re(CO)Cp* (10) without the observation of an intermediate. Reaction of 1 with CH3C=CCH3 at -60°C initially produced the 1:1 adduct Cp*(CO)2Re(μ-CO)Re(CO)(η2-CH 3C=CCH3)Cp* (8). At -40°C, the 2-butyne complex 8 slowly converted to a mixture of dimetallacyclopentenone Cp*(CO)2Re[μ-η13-(CH 3)C=C(CH3)CO]-Re(CO)Cp* (9) and two fragmentation products: Cp*Re(CO)3 and Cp*Re(CO)(CH3C≡CCH3) (14). At room temperature, 9 converted to additional Cp*Re(CO)3 and Cp*Re(CO)-(CH3C=CCH3) (14). A fluxional process that interchanges the environments of the Cp* groups and the methyl groups of Cp*(CO)2Re[μ-η13-(CH 3)C=C(CH3)CO]Re(CO)Cp* (9) is suggested to proceed via the dimetallacyclobutene intermediate Cp*(CO)2Re(μ-η11-CH 3C=CCH3)Re(CO)2Cp* (A).

Original languageEnglish
Pages (from-to)2640-2649
Number of pages10
JournalOrganometallics
Volume15
Issue number11
DOIs
Publication statusPublished - 1996 May 28
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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