Structures and Physical Properties of Chemically Reduced Diindenosiloles and Their π-Extended Derivatives

Structures and Physical Properties of Chemically Reduced Diindenosiloles and Their π-Extended Derivatives
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化学还原二茚并硅醇及其π-延伸衍生物的结构和物理性质

DOI:
10.1021/acs.organomet.7b00260
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发表时间:
2017
期刊:
影响因子:
2.8
通讯作者:
Nozaki Kyoko
Nozaki Kyoko
中科院分区:
化学2区
文献类型:
--
作者:
Takano Ryo;Shintani Ryo;Fukazawa Aiko;Yamaguchi Shigehiro;Nakabayashi Koji;Ohkoshi Shin-ichi;Nozaki Kyoko

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采用不同碱金属还原硅桥富瓦烯衍生物DiindenosiloleSi 1,得到其二价阴离子,并通过X射线晶体学分析对其结构进行了表征.还合成了Si 1的自由基阴离子和π-扩展的Si 3的二价阴离子,并系统地比较了它们的结构和物理性质。实验还发现,Si_(12-)和Si_(32-)的NMR谱的信号宽度具有反阳离子性和温度依赖性,表明可能存在闭壳层单重态和开壳层三重态之间的热相互转换。
DiindenosiloleSi1, a silicon-bridged fulvalene derivative, was successfully reduced to its dianions using various alkali metals, and the structures were characterized by X-ray crystallographic analysis. Radical anions ofSi1as well as dianions of π-extendedSi3could also be synthesized, and the structural and physical properties were systematically compared. It was also found that the NMR spectra of dianionsSi12–andSi32–show countercation and temperature dependency for their signal broadness, indicating the possible existence of thermal interconversion between closed-shell singlet states and open-shell triplet states.
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