著者
Michiyasu Sakagami Takahiro Sasamori Heisuke Sakai Yukio Furukawa Norihiro Tokitoh
出版者
(社)日本化学会
雑誌
Bulletin of the Chemical Society of Japan (ISSN:00092673)
巻号頁・発行日
vol.86, no.10, pp.1132-1143, 2013-10-15 (Released:2013-10-15)
参考文献数
62
被引用文献数
27

1,2-Bis(ferrocenyl)dipnictenes bearing a Pn=Pn π-spacer (Pn: P (1), Sb (2), and Bi (3)) between two ferrocenyl units have been synthesized as stable compounds. Not only their molecular structures and fundamental properties but also their redox behavior have been systematically disclosed. Interestingly, in the reduction region, the dipnictenes showed two pseudo-reversible one-electron redox couples at low temperature, suggesting possible generation of the corresponding radical anion and dianion species. On the other hand, they showed three-step one-electron oxidation processes in the oxidation region. The first two oxidation steps would correspond to those of the two ferrocenyl moieties, while the third step would be that of the Pn=Pn π-spacer moiety, respectively. Thus, these 1,2-bis(ferrocenyl)dipnictenes with a Pn=Pn π-spacer should be stable multiredox systems reflecting unique properties of a double bond between heavier 15 group elements. As a result, all Pn=Pn units (Pn: P, Sb, and Bi) were found to work as a more effective π-spacer than those of 2nd row elements such as C=C and N=N.
著者
Eiko Mieda Takahiro Sasamori Shohei Sase Kei Goto Norihiro Tokitoh
出版者
The Chemical Society of Japan
雑誌
Chemistry Letters (ISSN:03667022)
巻号頁・発行日
vol.40, no.2, pp.196-197, 2011-02-05 (Released:2011-01-22)
参考文献数
18

We report here the attempted synthesis of a stable 1-fluoro-2-hydrosilene bearing a Bpq group, which is a bulky aryl group bearing a cavity-shaped framework. We have successfully synthesized an overcrowded benzyldifluorosilane as a precursor. Treatment of the benzyldifluorosilane with 2 equiv of t-BuOK in THF afforded the corresponding benzyl anion, the structure of which showed a unique feature as a fluorosilene–KF complex.