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学科主题: 金属有机化学
题名: Cyclooctatetraene (COT)-coordinated diiron carbene complexes and their remarkable thermolysis reactions
其他题名: 环辛四烯配体的双铁卡宾络合物和它们的热解反应
作者: Zhang L(张磊) ; Zhang S(张庶) ; Xu Q(徐强) ; Xiao N(肖努) ; Sun J(孙杰) ; Chen JB(陈家碧)
通讯作者: 陈家碧
刊名: Organometallics
发表日期: 2005
卷: 24, 期:5, 页:933-944
收录类别: SCI
部门归属: 上海有机所; 日本工业科学技术研究所
英文摘要: The reactions of the COT-coordinated diiron cationic bridging carbyne complexes [Fe-2(mu-CAr)(CO)(4)(eta(8)-C8H8)]BF4 (1, Ar = C6H5; 2, Ar = p-CH3C6H4; 3, Ar = p-CF3C6H4) with p-methylaniline gave the COT-coordinated diiron Fischer-type carbene complexes [Fe-2{= C(Ar)NHC6H4CH3-p}(mu-CO)(CO)(3)(eta(8)-C8H8)] (7, Ar = C6H5; 8, Ar = p-CH3C6H4; 9, Ar = p-CF3C6H4). Heating the solution of diiron carbene complexes [Fe-2{=C(Ar)NHC6H5}(mu-CO)-(CO)(3)(eta(8)-C8H8)] (4, Ar = C6H5; 5, Ar = p-CH3C6H4; 6, Ar = p-CF3C6H4) in benzene in a sealed tube at 85-90degreesC for 72 h afforded the chelated diiron carbene complex [Fe-2{=C(C6H5)-NC6H5}(eta(2):eta(3):eta(2)-C8H9)(CO)(4)] (4a), C-8 ring addition products [Fe-2{N(C6H5)=C(Ar)(eta(1):eta(3):eta(2)-C8H9)}(CO)(5)] (10, Ar = C6H5; 12, Ar = p-CH3C6H4; 14, Ar = p-CF3C6H4), and C-7 contraction ring products [Fe-2{N(C6H5)=C(Ar)CH(eta(2):eta(3)-C7H8)(CO)(4)}] (11, Ar = C6H5; 13, Ar = p-CH3C6H4; 15, Ar = p-CF3C6H4), respectively. The similar thermolysis of complexes 7 and 8 afforded corresponding thermolysis products [Fe-2{=C(C6H5)NC6H4CH3-p}(eta(2):eta(3):eta(2)-C8H9)(CO)(4)] (7a), [Fe-2{N(C6H4CH3-p)=C(Ar)(eta(1):eta(2):eta(3)-C8H9)}(CO)(5)] (16, Ar = C6H5; 18, Ar = p-CH3C6H4), and [Fe-2{N(C6H4CH3-p)=C(Ar)CH(eta(2):eta(3)-C7H8)}(CO)(4)] (17, Ar = C6H5; 19, Ar = p-CH3C6H4), respectively. Interestingly, products 4a and 7a were transformed into the eight-membered ring products 10 and 16 and seven-membered ring products 11 and 17, respectively, under similar conditions. Surprisingly, compounds 10, 16, and 18 can also be partially transformed into compounds 11, 17, and 19, respectively, by further thermolysis at higher temperature (100-105degreesC). The structures of complexes 7, 10, 11, 18, and 19 have been established by X-ray diffraction studies.
语种: 英语
相关网址: 查看原文
WOS记录号: WOS:000227098200026
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内容类型: 期刊论文
URI标识: http://ir.sioc.ac.cn/handle/331003/21405
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 L,Zhang S,Xu Q,et al. Cyclooctatetraene (COT)-coordinated diiron carbene complexes and their remarkable thermolysis reactions[J]. Organometallics,2005,24(5):933-944.
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