Remarkable Nucleophilic Addition to and Ring Breaking of the Cycloheptatrienyl Ligand in Reactions of [μ-(1−3-η):(4−7-η)-Cycloheptatrienyl]tricarbonylirontricarbonylmanganese and -rhenium with Aryllithium Reagents
2002; American Chemical Society; Volume: 21; Issue: 18 Linguagem: Inglês
10.1021/om020328w
ISSN1520-6041
AutoresNu Xiao, Shu Zhang, Zhilei Qiu, Ronghua Li, Beihan Wang, Qiang Xü, Jie Sun, Jiabi Chen,
Tópico(s)Asymmetric Hydrogenation and Catalysis
ResumoThe reactions of [μ-(1−3-η):(4−7-η)-cycloheptatrienyl]tricarbonylirontricarbonylmanganese, [MnFe{μ-(1−3-η):(4−7-η)-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 novel ring-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 [μ-(1−3-η):(4−7-η)-cycloheptatrienyl]tricarbonylirontricarbonylrhenium, [ReFe{μ-(1−3-η):(4−7-η)-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 been established by single-crystal X-ray diffraction studies.
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