Reactions of the Titanaallene Intermediate [Cp*2TiCCH2] with Isonitriles: An Approach to the Chemistry of Radialene Type Molecules†
Reactions of the Titanaallene Intermediate [Cp*2TiCCH2] with Isonitriles: An Approach to the Chemistry of Radialene Type Molecules†
复制标题
二钛联烯中间体 [Cp*2TiCCH2] 与异腈的反应：辐射烯型分子的化学方法†
DOI：
10.1021/om000929s
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发表时间：
2001
期刊：
影响因子：
2.8
通讯作者：
I. Strauß
中科院分区：
文献类型：
--
作者：
C. Santamaría;R. Beckhaus;D. Haase;R. Koch;A. Saak;I. Strauß
由Cp* 2 Ti（CHCH 2）Me（1）经甲烷消除反应得到的钛丙二烯中间体[Cp* 2 TiCCH 2]（2）与过量的环己基异腈（CyNC）反应，得到具有轴烯亚结构的五元金属配合物（4）。该反应通过[2+1]加成，随后插入两个异腈分子而发生。从1与2，6-二甲基苯基异腈（ArNC）以1：2比例的反应中分离出[2+1]加成产物，其形式为氮杂丁三烯络合物[Cp* 2 Ti（CNAr）（η2-H2 CCCNAr）（5）。5的X射线结构分析揭示了由另一个ArNC配体稳定的η2-C，C-氮杂环丁三烯部分组成的五配位几何结构。而5在固态（dec 102−105 °C）下是稳定的，在溶液（20 °C）中释放出一个异腈分子。随后的分子内C-H键活化和C-C键形成得到产物7。后者可以直接从2与1当量的ArNC的反应中分离。对二茂钛化合物2的处理...
The titanaallene intermediate [Cp*2TiCCH2] (2), obtained via methane elimination from Cp*2Ti(CHCH2)Me (1), reacts with an excess of cyclohexylisonitrile (CyNC), to give the five-membered metallacycle (4), which exhibits a radialene substructure. This reaction occurs by a [2+1] addition followed by subsequent insertion of two molecules of isonitrile. A [2+1] addition product is isolated from the reaction of 1 with 2,6-dimethylphenylisonitrile (ArNC) in 1:2 ratio in the form of the azabutatriene complex [Cp*2Ti(CNAr)(η2-H2CCCNAr) (5). The X-ray structure analysis of 5 reveals a pentacoordinated geometry consisting of a η2-C,C-azabutatriene moiety stabilized by a further ArNC ligand. Whereas 5 is stable in the solid state (dec 102−105 °C), in solution (20 °C) one molecule of isonitrile is released. Subsequent intramolecular C−H bond activation and C−C bond formation afford product 7. The latter can be directly isolated from reaction of 2 with 1 equiv of ArNC. The treatment of the titanaallene species 2 with ...