Insertion and β-Hydride Elimination Reactions of Ruthenium/Zirconium Complexes Containing C2 Bridges with Bond Orders of 1, 2, and 3

Frederick R. Lemke, R. Morris Bullock

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

Carbon dioxide inserts into the Zr-C bond of Cp(PMe3)2RuCH═CHZrClCp2, producing the carboxylate complex Cp(PMe3)2RuCH═CHCO2ZrClCp2. An η2-iminoacyl insertion product, Cp(PMe3)2Ru—C≡C-C(NtBu)ZrClCp2, results from insertion of tBuNC into the Zr-C bond of the dimetalloalkyne complex Cp(PMe3)2Ru—C≡C—ZrClCp2. The reaction of Cp(PMe3)2RuCH2CH2ZrClCp2with high concentrations of tBuNC also produces an η2-immoacyl insertion product, Cp(PMe3) 2RuCH2CH2C(NtBu)ZrClCp2. At low concentrations of tBuNC, a competing reaction is β-hydride elimination from Cp(PMe3)2RuCH2CH2ZrClCp2to give Cp(PMe3)2RuCH=CH 2and Cp2Zr(H)Cl, which is trapped by tBuNC under these conditions to give Cp2ZrCl(η2-tBuN=CH). The reaction of benzophenone with Cp(PMe3)2RuCH2CH2ZrClCp2gives the insertion product Cp(PMe3)2RuCH2CH2CPh2OZrClCp2. β-Hydride elimination is also observed from Cp(PMe3)2RuCH═CHZrClCp2; in the presence of excess nBuC═CH, the products are Cp(PMe3)2Ru— C≡C—H and the zirconium vinyl complex Cp2Zr(Cl)CH═CHnBu.

Original languageEnglish
Pages (from-to)4261-4267
Number of pages7
JournalOrganometallics
Volume11
Issue number12
DOIs
Publication statusPublished - Dec 1 1992

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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