Reactions of Metallacyclopentadiene with Terminal Alkynes: Isolation and Characterization of Metallafulvenallene Complexes

Reactions of Metallacyclopentadiene with Terminal Alkynes: Isolation and Characterization of Metallafulvenallene Complexes
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金属环戊二烯与末端炔烃的反应:金属富烯配合物的分离和表征

DOI:
10.1021/acs.organomet.9b00371
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发表时间:
2019-07
期刊:
影响因子:
2.8
通讯作者:
Xia Haiping
Xia Haiping
中科院分区:
化学2区
文献类型:
--
作者:
Luo Ming;Deng Zhihong;Ruan Yonghong;Cai Yapeng;Zhuo Kaiyue;Zhang Hong;Xia Haiping

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金属环戊二烯在过渡金属催化的炔烃环三聚反应中起着重要的作用。这些独特的五元金属环的分离和表征有助于进一步了解相关的催化反应。在本工作中,通过稠合金属环戊二烯与末端炔的反应合成了第一个金属富烯配合物。单晶X-射线衍射谱和核磁共振谱的研究表明,该金属富烯配合物的双环骨架由一个金属环戊二烯和一个六元金属环组成,具有η1-亚甲基配体。通过氚标记实验,研究了稠合金属环戊二烯转化为稠合金属富烯的反应机理。测量了这些独特结构的紫外-可见吸收光谱。
Metallacyclopentadienes play an important role in transition-metal-catalyzed cyclotrimerization of alkynes. Isolation and characterization of these unique five-membered metallacycles could promote further understanding of related catalytic reactions. In this work, the first metallafulvenallene complexes were synthesized by the reaction of fused metallacyclopentadiene with terminal alkynes. Single-crystal X-ray diffraction and NMR spectroscopic studies on the metallafulvenallene complexes demonstrate that the bicyclic framework consists of a metallacyclopentadiene fused with a six-membered metallacycle, featuring an η1-vinylidene ligand. Deuterium labeling experiments were carried out to investigate the mechanism for the transformation of fused metallacyclopentadiene to fused metallafulvenallene. The UV–vis absorption spectra of these unique structures were measured.
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