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

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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)ZrClCp 2, 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)2RuCH2CH2ZrClCp2 with high concentrations of tBuNC also produces an η2-iminoacyl insertion product, Cp(PMe3)2RuCH2CH2C(N tBu)ZrClCp2. At low concentrations of tBuNC, a competing reaction is β-hydride elimination from Cp(PMe3)2RuCH2CH2ZrClCp2 to give Cp(PMe3)2RuCH=CH2 and Cp2Zr(H)Cl, which is trapped by tBuNC under these conditions to give Cp2ZrCl(η2-tBuN=CH). The reaction of benzophenone with Cp(PMe3)2RuCH2CH2ZrClCp2 gives the insertion product Cp(PMe3)2RuCH2CH2CPh 2OZrClCp2. 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
Publication statusPublished - 1992

Fingerprint

Ruthenium
Hydrides
ruthenium
hydrides
insertion
elimination
products
Carbon Dioxide
methylidyne
inserts
carboxylates
carbon dioxide
low concentrations
Schwartz reagent
benzophenone

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Insertion and β-hydride elimination reactions of ruthenium/zirconium complexes containing C2 bridges with bond orders of 1, 2, and 3. / Lemke, Frederick R.; Bullock, R Morris.

In: Organometallics, Vol. 11, No. 12, 1992, p. 4261-4267.

Research output: Contribution to journalArticle

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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)ZrClCp 2, 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)2RuCH2CH2ZrClCp2 with high concentrations of tBuNC also produces an η2-iminoacyl insertion product, Cp(PMe3)2RuCH2CH2C(N tBu)ZrClCp2. At low concentrations of tBuNC, a competing reaction is β-hydride elimination from Cp(PMe3)2RuCH2CH2ZrClCp2 to give Cp(PMe3)2RuCH=CH2 and Cp2Zr(H)Cl, which is trapped by tBuNC under these conditions to give Cp2ZrCl(η2-tBuN=CH). The reaction of benzophenone with Cp(PMe3)2RuCH2CH2ZrClCp2 gives the insertion product Cp(PMe3)2RuCH2CH2CPh 2OZrClCp2. 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.",
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N2 - 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)ZrClCp 2, 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)2RuCH2CH2ZrClCp2 with high concentrations of tBuNC also produces an η2-iminoacyl insertion product, Cp(PMe3)2RuCH2CH2C(N tBu)ZrClCp2. At low concentrations of tBuNC, a competing reaction is β-hydride elimination from Cp(PMe3)2RuCH2CH2ZrClCp2 to give Cp(PMe3)2RuCH=CH2 and Cp2Zr(H)Cl, which is trapped by tBuNC under these conditions to give Cp2ZrCl(η2-tBuN=CH). The reaction of benzophenone with Cp(PMe3)2RuCH2CH2ZrClCp2 gives the insertion product Cp(PMe3)2RuCH2CH2CPh 2OZrClCp2. 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.

AB - 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)ZrClCp 2, 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)2RuCH2CH2ZrClCp2 with high concentrations of tBuNC also produces an η2-iminoacyl insertion product, Cp(PMe3)2RuCH2CH2C(N tBu)ZrClCp2. At low concentrations of tBuNC, a competing reaction is β-hydride elimination from Cp(PMe3)2RuCH2CH2ZrClCp2 to give Cp(PMe3)2RuCH=CH2 and Cp2Zr(H)Cl, which is trapped by tBuNC under these conditions to give Cp2ZrCl(η2-tBuN=CH). The reaction of benzophenone with Cp(PMe3)2RuCH2CH2ZrClCp2 gives the insertion product Cp(PMe3)2RuCH2CH2CPh 2OZrClCp2. 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.

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