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学科主题: 金属有机化学
题名: Remarkable Reactions of Cyclooctatetraene Diiron-Bridging Carbyne Complexes with Amino and Amido Compounds. Nucleophilic Addition to and Breaking of Cyclooctatetraene Ring
其他题名: 环辛四烯双铁桥卡拜络合物 与氨基和胺基化合物的新奇反应: 环辛四烯环的亲核加成和破坏
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: Chem.-Eur. J.
发表日期: 2003-01-01
卷: 9, 期:20, 页:5111-5122
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 reactions of the cationic diiron-bridging carbyne complexes ?Fe2(μ-Car)(CO)4(η8-C8H8)]BF4 (1, Ar = C6H5; 2, Ar = p-CH3C6H4; 3, Ar = p-CF3C6H4) with LiN(C6H5)2 in THF at low temperature give novel N-nucleophilic-addition products, nanely, the neutral, diiron-bridging carbyne complexes [Fe2(μ-Car)(CO)4(?η7- C8H8N(C6H5)2)] (4, Ar = C6H5; 5, Ar = p-CH3C6H4; 6, Ar = p-CF3C6H4)). Cationic bridging carbyne complexes 1-3 react with (C2H5)2NH, (i-C3H7)2NH, and (C6H11)2NH under the same conditions with ring cleavage of the COT ligand to produce the novel diiron-bridging carbene inner salts [Fe2{?-C(Ar)C8H8NR2}(CO)4] (7, Ar = C6H5, R = C2H5; 8, Ar = p-CH3C6H4, R = C2H5; 9, Ar = p-CF3C6H4, R = C2H5; 10, Ar = C6H5, R = i-C3H7; 11, Ar = p-CH3C6H4, R = i-C3H7; 12, Ar = p-CF3C6H4, R = i-C3H7; 13, Ar = C6H5, R = C6H11; 14, Ar = p-CH3C6H4, R = C6H11, 15, Ar = p-CF3C6H4, R = C6H11). Piperidine reacts similarly with cationic carbyne complex 3 to afford the corresponding bridging carbene inner salt [Fe2{μ-C(Ar)C8H8N(CH2)5}(CO)4] (16). Compound 9 was transformed into a new diiron-bridging carbene inner salt 17, the trans isomer of 9, by heating in benzene. Unexpectedly, the reaction of C6H5NH2 with 2 gives a novel COT iron-carbene complex [Fe2{=C(C6H4CH3-p)NHC6H5}(μ-CO)- (CO)3(η8-C8H8)] (18). However, the analogous reactions of 2-naphthylamine with 2 and of p-CF3C6H4NH2 with 3 produce novel chelated iron-carbene complexes [Fe2{=C(C6H4CH3-p)NC10H7}(CO)4(η2:η3:η2-C8H9)] (19) and [Fe2{=C(C6H4CF3-p)- NC6H4CF3-p}(CO)4(η2:η3:η2-C8H9)] (20), respectively. Compound 18 can also be transformed into the analogous chelated iron-carbene complex [Fe2{=C(C6H4CH3-p)- NC6H5}(CO)4(η2:η3:η2-C8H9)] (21). The structures of complexes 6, 9, 15, 17, 18 and 21 have been established by X-ray diffraction studies.
语种: 英语
相关网址: 查看原文
内容类型: 期刊论文
URI标识: http://ir.sioc.ac.cn/handle/331003/21393
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. Remarkable Reactions of Cyclooctatetraene Diiron-Bridging Carbyne Complexes with Amino and Amido Compounds. Nucleophilic Addition to and Breaking of Cyclooctatetraene Ring[J]. Chem.-Eur. J.,2003,9(20):5111-5122.
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