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学科主题: 金属有机化学
题名: Unusual reactions of cationic bridging carbyne complexes of dimethylsilane-bridged bis(η~5-cyclopentadienyl)diiron tricarbonyl with carbonylmetal anions
其他题名: 二甲基硅烷桥联的双(η~5-环戊二烯基)三羰基双铁阳离子桥卡拜络合物与羰基金属阴离子的新奇反应
作者: Wang RT(王锐涛) ; Sun J(孙杰) ; Chen JB(陈家碧) ; Xu Q(徐强) ; Yoshie Souma
通讯作者: 陈家碧
刊名: J. Organomet. Chem.
发表日期: 2002-01-01
卷: 658, 期:1-2, 页:214-227
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; 日本产业技术综合研究所
英文摘要: The reactions of he dimethylsilane-bridged cationic carbyne complexes of diiron, [Fe^2(μ-Car)(CO)^2 [η~5-C^5H^4Si(CH^3)^2}BBr^4(1,Ar=C^6H^5; 2, Ar=Pcf^3H^4), with carbonylmetal anionic compounds Na[M(CO)^5CN](4,M=Cr;5, M=Mo; 6, M=W) in THF at low temperature afford diiron bridging carbene complexes [Fe^2(μ-(CO)){μ-C(Ar)NCM(CO)^5}(CO)^2{(η~5-C^5H^4)^2Si(CH^3)^2}](9, M=Cr, Ar=C^6H^5; 10, M =Mo, Ar=C^6H^5; ; 11, M=W,Ar=C^6H^5; 12, M=Cr, Ar=p-CF^3C^6H^4; 13, M=Mo, Ar=p-CF^3C^6H^4; 14, M=W, Ar=p-CF^3C^6H^4). In contrast to the reaction of 1 and 2 cationic carbyne complex [Fe^2(μ-CO)(μ-CC^6H4CH^3-p)(CO)^2{(η~5-C^5H^4)^2Si(CH^3)^2}]BBr^4(3) reacts with 4-6 under the same conditions to produce novel cationic bridging carbyne complexes [Fe^2(μ-CO)(μ-CC^6H4CH^3-p)(CO)^2{(η~5-C^5H^4)^2Si(CH^3)^2}]+[M(CO)^5CN]-(15,M=CR; 16,M=MO; 17,M=W). Analogous cationic bridging carbyne complex [[Fe^2(μ-CO)(μ-CC^6H4CH^3-p)(CO)^2{(η~5-C^5H^4)^2Si(CH^3)^2}+[Fe(CO)^4CN]-(18) can also be obtained from the reaction of 3 with Na[Fe(CO)^4CN] (7). Complex 15 or 16 reacts with NaSR (R=CH^3, C^6H^5, p-CH^3C^6H^4) to give bridging mercaptocarbene complexes [Fe^2(μ-CO){μ-C(SR)C^6H^4CH^3-p} (CO)^2{η~5-C^5H^4)^2Si(CH^3)^3}] (19, R=CH^3; 20, R=C^6H^5; 21, R=p-CH^3C^6H^4) in high yields. The related reaction of 1 with NaN(SiMe^3)^2 affords a novel benzonitrile-coordinated diiron complex [[Fe^2(μ-CO^2(CO)NCC^6H^5{η~5-C^5H^4)^2Si(CH^3)^2}] (22). Unexpectedly, the reactions of 1 and 2 with 7 yield diiron bridging arylcarbene comlexes [Fe^2(μ-CO){μC(H)Ar}(CO)^2{(η~5-C^5H^4)^2Si(CH^3)^2}](23, Ar=C^6H^5; 24, Ar=p-CF^3C^6^H^4). The products 23 and 24 and bridging p-tolyl-carbene complex [Fe^2(μ-CO){μ-(CO){μ-C(H)C^6H^4CH^3-p}(CO)^2{η~5-C^5H^4)^2Si(CH^3)^2}] (2) were also obtained from the reactions of 1-3 with [PPh^3)^2N][Cr(CO)^4NO] (8). The structures of 14.15,22, and 23 have been established by X-ray crystallography.
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/331003/21385
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:
Wang RT,Sun J,Chen JB,et al. Unusual reactions of cationic bridging carbyne complexes of dimethylsilane-bridged bis(η~5-cyclopentadienyl)diiron tricarbonyl with carbonylmetal anions[J]. J. Organomet. Chem.,2002,658(1-2):214-227.
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