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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
Zhang S(张庶); Xu Q(徐强); Sun J(孙杰); Chen JB(陈家碧)
2003
发表期刊Chem.-Eur. J.
ISSN0947-6539
卷号9期号:20页码:5111-5122
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.
学科领域金属有机化学
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
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收录类别SCI
语种英语
文献类型期刊论文
条目标识符http://ir.sioc.ac.cn/handle/331003/21393
专题金属有机化学国家重点实验室
通讯作者Xu Q(徐强); Chen JB(陈家碧)
推荐引用方式
GB/T 7714
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.
APA 张庶,徐强,孙杰,&陈家碧.(2003).Remarkable Reactions of Cyclooctatetraene Diiron-Bridging Carbyne Complexes with Amino and Amido Compounds. Nucleophilic Addition to and Breaking of Cyclooctatetraene Ring.Chem.-Eur. J.,9(20),5111-5122.
MLA 张庶,et al."Remarkable Reactions of Cyclooctatetraene Diiron-Bridging Carbyne Complexes with Amino and Amido Compounds. Nucleophilic Addition to and Breaking of Cyclooctatetraene Ring".Chem.-Eur. J. 9.20(2003):5111-5122.
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