Reaction of Cp*(CO)2Re=Re(CO)2Cp* with Alkynes Produces Dimetallacyclopentenones Cp*(CO)2Re(-![]()
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- 作者：Charles P. Casey ; Ronald S. Cariñ ; o ; and Hiroyuki Sakaba
- 刊名：Organometallics
- 出版年：1997
- 出版时间：February 4, 1997
- 年：1997
- 卷：16
- 期：3
- 页码：419 - 426
- 全文大小：474K
- 年卷期：v.16,no.3(February 4, 1997)
- ISSN：1520-6041
文摘
Cp*(CO)2Re=Re(CO)2Cp*(1) reacted with terminal alkynes HC
CR (R = H,CH3, C6H5,C(CH3)=CH2,OCH2CH3) to producedimetallacyclopentenonesCp*(CO)2Re(
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1,3-CH=CRCO)Re(CO)Cp* (4-8). Thereaction of 1 with alkynes having one ester substituent alsogavedimetallacyclopentenones. Reaction of 1 withHCCCO2Me gaveCp*(CO)2Re[-1,3-CH=C(CO2CH3)CO]Re(CO)Cp* (9)and with CH3CCCO2Me gaveCp*(CO)2Re[-1,3-(CO2CH3)C=C(CH3)CO]Re(CO)Cp*(10). At low temperature, the 2-propynecomplex Cp*(CO)2Re(-CO)Re(CO)(HCCCH3)Cp*(12) andCp*(CO)2Re[-1,3-C(CH3)=CHCO]Re(CO)Cp*(11) were observed as intermediates in the formation ofCp*(CO)2Re[-1,3-CH=C(CH3)CO]Re(CO)Cp* (5). Protonation ofdimetallacyclopentenone 2 withCF3CO2H produced[Cp*(CO)2Re(-1,2-CH=CH2)Re(CO)2Cp*]+CF3CO2-(14), a species with a bridging vinylgroup. Protonation of the thermodynamically favored regioisomericdimetallacyclopentenone5 gave[Cp*(CO)2Re(-1,2-(E)-CH=CHCH3)Re(CO)2Cp*]+CF3CO2-(15). Protonation ofkinetically formed regioisomeric dimetallacyclopentenone 11at low temperature gave [Cp*(CO)2Re(-1,2-CCH3=CH2)Re(CO)2Cp*]+CF3CO2-(16).
CR (R = H,CH3, C6H5,C(CH3)=CH2,OCH2CH3) to producedimetallacyclopentenonesCp*(CO)2Re(-1,3-CH=CRCO)Re(CO)Cp* (4-8). Thereaction of 1 with alkynes having one ester substituent alsogavedimetallacyclopentenones. Reaction of 1 withHCCCO2Me gaveCp*(CO)2Re[-1,3-CH=C(CO2CH3)CO]Re(CO)Cp* (9)and with CH3CCCO2Me gaveCp*(CO)2Re[-1,3-(CO2CH3)C=C(CH3)CO]Re(CO)Cp*(10). At low temperature, the 2-propynecomplex Cp*(CO)2Re(-CO)Re(CO)(HCCCH3)Cp*(12) andCp*(CO)2Re[-1,3-C(CH3)=CHCO]Re(CO)Cp*(11) were observed as intermediates in the formation ofCp*(CO)2Re[-1,3-CH=C(CH3)CO]Re(CO)Cp* (5). Protonation ofdimetallacyclopentenone 2 withCF3CO2H produced[Cp*(CO)2Re(-1,2-CH=CH2)Re(CO)2Cp*]+CF3CO2-(14), a species with a bridging vinylgroup. Protonation of the thermodynamically favored regioisomericdimetallacyclopentenone5 gave[Cp*(CO)2Re(-1,2-(E)-CH=CHCH3)Re(CO)2Cp*]+CF3CO2-(15). Protonation ofkinetically formed regioisomeric dimetallacyclopentenone 11at low temperature gave [Cp*(CO)2Re(-1,2-CCH3=CH2)Re(CO)2Cp*]+CF3CO2-(16).