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Serendipity in unexpected reactions of group 4 metallocene Bis(trimethylsilyl)acetylene complexes and its consequences for selected applications
Journal of Organometallic Chemistry ( IF 2.3 ) Pub Date : 2019-12-09 , DOI: 10.1016/j.jorganchem.2019.121071
U. Rosenthal

Examples for serendipity in several unexpected reactions of group 4 metallocene bis(trimethylsilyl)acetylene complexes are summarized in this Review. The first is the reaction of Cp2Ti (η2-btmsa) with tolane, PhC≡CPh, investigated 1988 in the Nesmeyanov Institute in Moscow giving surprisingly no coupling of Me3SiC≡CSiMe3 with PhC≡CPh to a titanacyclopentadiene but the substitution of bis(trimethylsilyl)acetylene by tolane and via the assumed alkyne complex Cp2Ti (η2-PhC2Ph) a C–C coupling reaction of two molecules of tolane to the tetraphenyl substituted titanacyclopentadiene (i). This simple substitution reaction of Cp2Ti (η2-btmsa) and of similar complexes was used for the generation of the very reactive coordinatively and electronically unsaturated complex fragments [Cp’2M]. The reaction of this complex with carbon dioxide gave a coupling with Me3SiC≡CSiMe3 to an unexpected dinuclear complex with relevance to the general mechanism of CO2 coupling reactions (ii). Furthermore it was demonstrated, that the Cp ligands in [Cp2Ti] were not inert, showing a rare type of coupling reaction with alkynes or ring opening reactions together with C–C coupling reactions of diynes (iii). Some other unexpected reactions were found with di- or polyynes. Depending on the ligands L (Cp’ = Cp, Cp* etc.), metals M (M = Ti, Zr, Hf) and the substrate substituents R (R = Me3Si, aryl, alkyl etc.) 1,3-butadiynes RC≡C–C≡CR react with [Cp’2M] under C–C bond cleavage of the internal C–C single bond (iv) or through complexation to unusual metallacyclocumulenes (v). The reverse reaction of C–C coupling of alkynyl groups to give coordinated 1,3-butadiynes in metallacyclocumulenes was described for some bis(acetylides) Cp’2Zr (-C≡CR)2 (vi). With polyynes R-(CC)n-R a sliding of the [Cp’2M] unit at the triple bonds was observed (vii).

All these unexpected examples (i) - (vii) represent reactions that were found by coincidence. Later several applications for the initial results were described. For this overview only one selected examples for these developments are described to illustrate the consequences of each of these results.



中文翻译:

第4组茂金属双(三甲基甲硅烷基)乙炔配合物的意外反应中的偶然性及其对某些应用的后果

本综述总结了第4组茂金属双(三甲基甲硅烷基)乙炔配合物的一些意外反应中的偶发性实例。首先是Cp的反应2的Ti(η 2 -btmsa)与二苯乙炔,PhC≡CPh,在莫斯科给出奇没有耦合的Me在Nesmeyanov研究所研究1988 3 SiC≡CSiMe 3与PhC≡CPh到titanacyclopentadiene但双(三甲基甲硅烷基)乙炔通过二苯基乙炔和取代经由所述假定炔复杂的Cp 2的Ti(η 2 -PhC 2二苯基乙炔的两个分子的四苯基取代titanacyclopentadiene PH)的C-C偶联反应()。Cp的这个简单的取代反应2的Ti(η 2 -btmsa)和类似的复合物被用于非常活泼的配位且电子不饱和复杂片段[CP”的生成2 M]。此复合物与二氧化碳的反应,得到与我的联接3 SiC≡CSiMe 3意外双核配合物与相关性CO的一般机构2偶联反应(II)。此外,已证明[Cp 2 Ti]中的Cp配体不是惰性的,显示出罕见的与炔烃的偶联反应或开环反应以及二炔的C–C偶联反应(iii)。发现二炔或多炔存在其他一些意想不到的反应。取决于配体L(Cp'= Cp,Cp *等),金属M(M = Ti,Zr,Hf)和底物取代基R(R = Me 3 Si,芳基,烷基等)1,3- butadiynesRC≡C-C≡CR与反应[CP” 2 M]下的内部的C-C单键的C-C键断裂(IV),或者通过络合到异常metallacyclocumulenes(v)。C-C的炔基基团的偶联的逆反应,得到协调,metallacyclocumulenes 1,3- butadiynes对于一些双(乙炔化物)CP”被描述2的Zr(-C≡CR)2VI)。与polyynes R-(C C)ñ -R滑动的[CP”的2观察到三键处的M]单元(vii)。

所有这些意想不到的例子(i)-(vii)表示巧合发现的反应。稍后描述了一些用于初始结果的应用程序。对于本概述,仅描述了这些开发的一个选定示例,以说明每个结果的后果。

更新日期:2019-12-11
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