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 language | English |
|---|---|
| Pages (from-to) | 4261-4267 |
| Number of pages | 7 |
| Journal | Organometallics |
| Volume | 11 |
| Issue number | 12 |
| Publication status | Published - 1992 |
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ASJC Scopus subject areas
- Inorganic Chemistry
- Organic Chemistry
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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 journal › Article
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TY - JOUR
T1 - Insertion and β-hydride elimination reactions of ruthenium/zirconium complexes containing C2 bridges with bond orders of 1, 2, and 3
AU - Lemke, Frederick R.
AU - Bullock, R Morris
PY - 1992
Y1 - 1992
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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UR - http://www.scopus.com/inward/citedby.url?scp=0013472699&partnerID=8YFLogxK
M3 - Article
AN - SCOPUS:0013472699
VL - 11
SP - 4261
EP - 4267
JO - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 12
ER -