Reactivity of Group 4 Metal Alkyl and Metallacyclic Compounds Supported by Aryloxide Ligands Toward Organic Isocyanides
Reactivity of Group 4 Metal Alkyl and Metallacyclic Compounds Supported by Aryloxide Ligands Toward Organic Isocyanides
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芳氧基配体支持的第 4 族金属烷基和金属环化合物对有机异氰化物的反应活性
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发表时间：
1999
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通讯作者：
I. Rothwell
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作者：
M. Thorn;P. Fanwick;I. Rothwell
本文研究了二甲基化合物[Ti（OC_6H_3Ph_2 - 2，6）_2Me_2]（1）和钛双环化合物[（ArO）_2Ti（CH_2CH（C_4H_8）CHCH_2）]（6，7）（由1，7-辛炔反式偶联而成）对有机异腈的反应性。二甲基1与1当量的2，6-二甲基苯基异氰化物（xyNC）反应生成环化产物[Ti（OC 6 H3 Ph 2 - 2，6）（OC 6 H3 Ph-η1-C6 H4）{N（xy）CHMe 2}]（2），其结构被表征。据信化合物2经由中间体η2-亚胺（氮杂环丙烷）内的CH键活化而产生，所述中间体η2-亚胺（氮杂环丙烷）通过两个甲基基团转移至异氰化物而形成。当xyNC过量时，1产生中间体双（η2-亚氨基酰基）4，其缓慢转化为烯二酰胺[Ti（OC 6 H3 Ph 2 - 2，6）2{N（xy）CMeCMeN（xy）}]（5）。5的固态结构显示存在由两个亚氨基酰基的分子内偶联形成的折叠的diazatitanacyclopyrene-3-ene环。钛双环化合物6和7分别与ButNC和xyNC反应生成产物8和9，它们都是可降解的。
The reactivity of the dimethyl compound [Ti(OC6H3Ph2-2,6)2Me2] (1) and titanabicyclic compounds [(ArO)2Ti(CH2CH(C4H8)CHCH2)] (6, 7) (formed by trans-coupling of 1,7-octadiene) toward organic isocyanides has been investigated. Dimethyl 1 reacts with 1 equiv of 2,6-dimethylphenylisocyanide (xyNC) to produce a cyclometalated product [Ti(OC6H3Ph2-2,6)(OC6H3Ph-η1-C6H4){N(xy)CHMe2}] (2), which was structurally characterized. Compound 2 is believed to arise via CH bond activation within an intermediate η2-imine (azatitanacyclopropane) formed by transfer of both methyl groups to the isocyanide. With an excess of xyNC, 1 produces an intermediate bis(η2-iminoacyl) 4, which slowly converts to the enediamide [Ti(OC6H3Ph2-2,6)2{N(xy)CMeCMeN(xy)}] (5). The solid-state structure of 5 shows the presence of a folded diazatitanacyclopent-3-ene ring formed by intramolecular coupling of the two iminoacyl groups. Titanabicyclic compounds 6 and 7 react with ButNC and xyNC respectively to generate products 8 and 9, which both c...