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学科主题: 金属有机化学
题名: Novel Reactions of Cyclooctatetraene (COT)-Coordinated Diiron Cationic Bridging Carbyne Complexes with Nucleophiles
其他题名: 环辛四烯(COT)配位的双铁阳离子桥卡拜络合物与亲核试剂的新奇反应
作者: Zhang S(张庶) ; Xu Q(徐强) ; Sun J(孙杰) ; Chen JB(陈家碧)
通讯作者: 徐强 ; 陈家碧
刊名: Organometallics
发表日期: 2003
卷: 22, 期:9, 页:1816-1826
收录类别: SCI
部门归属: 中国科学院上海有机化学研究所金属有机化学开放实验室;日本产业技术研究所
英文摘要: The COT-coordinated diiron cationic bridging carbyne complexes,Fe2(μ-Car)(CO)4(η8-C8H8)]BF4 (1, Ar = C6H5; 2, Ar = p-CH3C6H4; 3, Ar = p-CF3C6H4) were prepared by the reactions of the diiron bridging alkoxycarbene complexes, ?Fe2{μ-C(OC2H5)Ar}(CO)4(η8-C8H8)?, with HBF4?Et2O at low temperature. Cationic 3 reacts with NaSR (R = C2H5, p-CH3C6H4) in THF at low temperature to afford diiron bridging sulfonylcarbene complexes ?Fe2{μ-C(SO2R)C6H4CF3-p}-(CO)4(η8-C8H8)] (7, R = C2H5; 8, R = p-CH3C6H4), while the reactions of 1-3 with NaBH4 under the similar conditions gave diiron bridging arylcarbene complexes ?Fe2{μ-C(H)Ar}(CO)4(η8-C8H8)] (9, Ar = C6H5; 10, Ar = p-CH3C6H4; 11, Ar = p-CF3C6H4). Complexes 1-3 can also react with anionic carbonylmetal compounds Na[M(CO)5CN] (4, M = Cr; 5, M = Mo; 6, M = W) to produce diiron bridging aryl(pentacarbonylcyanometal)carbene complexes ?Fe2{μ-C(Ar)NCM(CO)5}-(CO)4(η8-C8H8)] (12, Ar = C6H5, M = Cr; 13, Ar = p-CH3C6H4, M = Cr; 14, Ar = p-CF3C6H4, M = Cr; 15, Ar = C6H5, M = Mo; 16, Ar = p-CH3C6H4, M = Mo; 17, Ar = p-CF3C6H4, M = Mo; 18, Ar = C6H5, M = W; 19, Ar = p-CH3C6H4, M = W; 20, Ar = p-CF3C6H4, M = W). Unexpectedly, aniline and 2-naphthylamine react with cationic 1 and 3 to give novel COT-coordinated iron carbene complexes [Fe2{=C(Ar)NHAr'}(μ-CO)(CO)3(η8-C8H8)] (21, Ar = C6H5, Ar' = C6H5; 22, Ar = p-CF3C6H4, Ar'?= C6H5; 23, Ar = p-CF3C6H4, Ar= 2-naphthyl). In solution, products 21-23 were transformed into chelated iron carbene complexes [Fe2{=C(Ar)Nar'}(CO)4η2:η3:η2-C8H9)] (24, Ar = C6H5, Ar'? = C6H5; 25, Ar = p-CF3C6H4, Ar'? = C6H5; 26, Ar = p-CF3C6H4, Ar' = 2-naphthyl) in high yields. The structures of complexes 7, 8, 11, 14, 15, 20, 22, and 24 have been established by X-ray diffraction studies.
语种: 英语
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WOS记录号: WOS:000182499400008
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内容类型: 期刊论文
URI标识: http://ir.sioc.ac.cn/handle/331003/21395
Appears in Collections:金属有机化学国家重点实验室_期刊论文

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Recommended Citation:
Zhang S,Xu Q,Sun J,et al. Novel Reactions of Cyclooctatetraene (COT)-Coordinated Diiron Cationic Bridging Carbyne Complexes with Nucleophiles[J]. Organometallics,2003,22(9):1816-1826.
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