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1-Zirconacyclobuta-2,3-dienes: synthesis of organometallic analogs of elusive 1,2-cyclobutadiene, unprecedented intramolecular C–H activation, and reactivity studies
Chemical Science ( IF 7.6 ) Pub Date : 2021-11-23 , DOI: 10.1039/d1sc06052j
Xinzhe Shi 1 , Sihan Li 1 , Melanie Reiß 1 , Anke Spannenberg 1 , Thorsten Holtrichter-Rößmann 2 , Fabian Reiß 1 , Torsten Beweries 1
Affiliation  

The structure, bonding, and reactivity of small, highly unsaturated ring systems is of fundamental interest for inorganic and organic chemistry. Four-membered metallacyclobuta-2,3-dienes, also referred to as metallacycloallenes, are among the most exotic examples for ring systems as these represent organometallic analogs of 1,2-cyclobutadiene, the smallest cyclic allene. Herein, the synthesis of the first examples of 1-zirconacyclobuta-2,3-dienes of the type [Cp′2Zr(Me3SiC3SiMe3)] (Cp′2 = rac-(ebthi), (ebthi = 1,2-ethylene-1,1′-bis(η5-tetrahydroindenyl)) (2a); rac-Me2Si(thi)2, thi = (η5-tetrahydroindenyl), (2b)) is presented. Both complexes undergo selective thermal C–H activation at the 7-position of the ansa-cyclopentadienyl ligand to produce a new type of “tucked-in” zirconocene system, 3a and 3b, that possesses a η3-propargyl/allenyl ligand. Both types of complexes react with carbonyl compounds, producing enynes in the case of 2a and 2b, as well as η1-allenyl complexes for 3a and 3b. Computational analysis of the structure and bonding of 2a and 3a reveals significant differences to a previously described related Ti complex. All complexes were fully characterised, including X-ray crystallography and experimental results were supported by DFT analysis.

中文翻译:

1-Zirconacyclobuta-2,3-dienes:合成难以捉摸的 1,2-环丁二烯的有机金属类似物、前所未有的分子内 C-H 活化和反应性研究

小的、高度不饱和的环系统的结构、键合和反应性是无机和有机化学的基础。四元金属环丁二烯,也称为金属环丙二烯,是环系统最奇特的例子之一,因为它们代表最小的环状丙二烯 1,2-环丁二烯的有机金属类似物。在此,[Cp' 2 Zr(Me 3 SiC 3 SiMe 3 )] (Cp' 2 = rac -(ebthi), (ebthi = 1 ,2-乙烯-1,1'-双(η 5 -四氢茚基)) ( 2a ); rac -Me 2 Si(thi)在图2中,表示thi=(η 5 -四氢茚基),( 2b ))。两种配合物都在ansa -环戊二烯基配体的 7 位进行选择性热 C-H 活化,从而产生一种新型的“嵌入”锆茂体系3a3b,它具有 η 3 -炔丙基/烯基配体。两种类型的配合物都与羰基化合物反应,在2a2b的情况下产生烯炔,以及在3a3b的情况下产生 η 1 -丙二烯基配合物。2a3a结构和键合的计算分析揭示了与先前描述的相关钛复合物的显着差异。所有配合物都得到了充分表征,包括 X 射线晶体学,实验结果得到了 DFT 分析的支持。
更新日期:2021-12-01
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