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学科主题: 金属有机化学
题名: Studies on thermolysis of isomerized products of olefin-cordinated alkoxycarbene iron complexes. Novel thermilytic products and their structures
其他题名: 烯烃配位的烷氧基卡宾铁络合物的异构化产物的热解反应研究
作者: Xiao N(肖努) ; Wang BH(王蓓含) ; Yin JG(殷建国) ; Xu Q(徐强) ; Sun J(孙杰) ; Chen JB(陈家碧)
通讯作者: 陈家碧
刊名: Organometallics
发表日期: 2004-01-01
卷: 23, 期:2, 页:257-268
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
英文摘要: Heating a solution of the isomerized (butadiene)(alkoxycarbene)iron complexes [C4H6(CO)2FeC(OC2H5)Ar] (1, Ar = o-CH3C6H4; 2, Ar = p-CF3C6H4) in benzene in a sealed tube at 70-80?C for 70-72 h gave the H-migrating pyrolytic products [{1-4-η-C4H5C(H)(OC2H5)C6H4CH3-o}Fe(CO)3] (15) and [{2-5-η-CH3C4H3(OC2H5)- C6H4CF3-p}Fe(CO)3] (16), respectively. A similar thermolysis of [C4H6(CO)2- {P(Oph)3}FeC(OC2H5)C6H4CF3-p] (3), a P(Oph)3 adduct of 2, yielded the analogous thermolytic products [{2-5-η-CH3C4H3(OC2H5)C6H4CF3-p}Fe(CO)2{P(Oph)3}] (17). The ring-opened (cycloheptatriene)(alkoxycarbene)iron complex [C7H8(CO)2FeC-(OC2H5)C6H4CH3-o] (4) was heated similarly to give the conjugating polyolefin-coordinated tricarbonyliron compound [{1-2-η):7-8-η)-C7H8C(OC2H5)C6H4CH3-o}-Fe(CO)3] (18), while the thermal decomposition of the ring-opened norbornadiene alkoxycarbene complexes [η3-C7H8(CO)2FeC(OC2H5)Ar] (5, Ar = C6H5; 6, Ar = p-CH3C6H4; 7, Ar = o-CH3C6H4; 8, Ar = p-CF3C6H4) afforded the novel diiron dimers [{Fe(μ-CO)(CO)(η5-C5H4CH2CH2-COAr)}2] (19, Ar = C6H5; 20, Ar = p-CH3C6H4) or C-C bond-breaking η4 olefin-coordinated tricarbonyliron complexes [{η4-C7H8C-(OC2H5)Ar}Fe(CO)3] (21, Ar = o-CH3C6H4; 22, Ar = p-CF3C6H4). The isomerized (limonene)(alkoxycarbene)iron complex [η3-C10H16(CO)2FeC(OC2H5)C6H5] (9) was thermally decomposed to produce theη4 cyclic olefin coordinated tricarbonyliron complex [{η4-C10H15CH(OC2H5)C6H5}Fe(CO)3] (23). Interestingly, the thermolysis of the (limonene)(alkoxycarbene)iron complex [η4-C10H16(CO)2FeC(OC2H5)C6H4CH3-o] (10) can also give the analogous cyclic olefin coordinated tricarbonyliron complex [{η4-C10H15CH(OC2H5)C6H4CH3-o}Fe(CO)3] (24). The thermolysis of the isomerized 1,5-cyclooctadiene(trimethylsiloxy)carbene iron complex [(CO)2Fe{η6-p-C6H5C6H4C-(OSiMe3)C8H12}] (11) yields 9-aryl-9-(trimethylsiloxy)bicyclo[4.2.1]non-2-ene, [p-C6H5C6H4C{Osi(CH3)3}C8H12] (25). The thermolyses of the isomerized products of the (cyclooctatetraene)(ethoxycarbene)iron complexes [η3-C8H8(CO)2FeC(OC2H5)Ar] (12, Ar = o-CH3C6H4; 13, Ar = C6H5) and [η4-C8H8(CO)2FeC(OC2H5)C6H4CH3-p] (14) produced the head-bridged cyclooctatriene derivatives [C8H8C(OC2H5)C6H4CH3-o] (26) and [C8H7(OC2H5)C(H)Ar] (27, Ar = C6H5; 28, Ar = p-CH3C6H4), respectively, via C-C bond formation or ethoxy migration. The structures of compounds 15-17, 20, 23, 25, 26, and 28 were 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/331003/21401
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Recommended Citation:
Xiao N,Wang BH,Yin JG,et al. Studies on thermolysis of isomerized products of olefin-cordinated alkoxycarbene iron complexes. Novel thermilytic products and their structures[J]. Organometallics,2004,23(2):257-268.
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