Remarkable Nucleophilic Addition to and Ring Breaking of the Cycloheptatrienyl Ligand in Reactions of [-(1-3-
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- 作者：Nu Xiao ; Shu Zhang ; Zhilei Qiu ; Ronghua Li ; Beihan Wang ; Qiang Xu ; Jie Sun ; and Jiabi Chen
- 刊名：Organometallics
- 出版年：2002
- 出版时间：September 2, 2002
- 年：2002
- 卷：21
- 期：18
- 页码：3709 - 3715
- 全文大小：160K
- 年卷期：v.21,no.18(September 2, 2002)
- ISSN：1520-6041
文摘
The reactions of [
-(1-3-
):(4-7-)-cycloheptatrienyl]tricarbonylirontricarbonylmanganese,[MnFe{-(1-3-):(4-7-)-C7H7}(CO)6] (1) with 2 molar equiv of aryllithium reagent, ArLi(Ar = C6H5, o-, m-, p-CH3C6H4), in ether at low temperature gave acylmetalate intermediates,followed by alkylation with Et3OBF4 in aqueous solution at 0 
C to afford the four novelring-opened olefin-coordinated tricarbonylirontricarbonylmanganese complexes [MnFe{C8H7(OC2H5)Ar}(CO)6] (3, Ar = C6H5; 4, Ar = o-CH3C6H4; 5, Ar = m-CH3C6H4; 6, Ar = p-CH3C6H4).Analogous reactions of [-(1-3-):(4-7-)-cycloheptatrienyl]tricarbonylirontricarbonylrhenium,[ReFe{-(1-3-):(4-7-)-C7H7)}(CO)6] (2), with ArLi (Ar = C6H5, o-, m-CH3C6H4, p-CF3C6H4)gave the corresponding products [ReFe{C8H7(OC2H5)Ar}(CO)6] (7, Ar = C6H5; 8, Ar =o-CH3C6H4; 9, Ar = m-CH3C6H4; 10, Ar = p-CF3C6H4). The structures of 4 and 10 have beenestablished by single-crystal X-ray diffraction studies.
-(1-3-):(4-7-)-cycloheptatrienyl]tricarbonylirontricarbonylmanganese,[MnFe{-(1-3-):(4-7-)-C7H7}(CO)6] (1) with 2 molar equiv of aryllithium reagent, ArLi(Ar = C6H5, o-, m-, p-CH3C6H4), in ether at low temperature gave acylmetalate intermediates,followed by alkylation with Et3OBF4 in aqueous solution at 0 C to afford the four novelring-opened olefin-coordinated tricarbonylirontricarbonylmanganese complexes [MnFe{C8H7(OC2H5)Ar}(CO)6] (3, Ar = C6H5; 4, Ar = o-CH3C6H4; 5, Ar = m-CH3C6H4; 6, Ar = p-CH3C6H4).Analogous reactions of [-(1-3-):(4-7-)-cycloheptatrienyl]tricarbonylirontricarbonylrhenium,[ReFe{-(1-3-):(4-7-)-C7H7)}(CO)6] (2), with ArLi (Ar = C6H5, o-, m-CH3C6H4, p-CF3C6H4)gave the corresponding products [ReFe{C8H7(OC2H5)Ar}(CO)6] (7, Ar = C6H5; 8, Ar =o-CH3C6H4; 9, Ar = m-CH3C6H4; 10, Ar = p-CF3C6H4). The structures of 4 and 10 have beenestablished by single-crystal X-ray diffraction studies.