Reactivity of an Acyclic Silylsilylene toward Ethylene: Migratory Insertion into the Si–Si Bond
Reactivity of an Acyclic Silylsilylene toward Ethylene: Migratory Insertion into the Si–Si Bond
复制标题
无环硅基亚甲硅基对乙烯的反应性：迁移插入到 Si-Si 键中
DOI：
10.1021/acs.organomet.5b00797
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发表时间：
2016
期刊：
影响因子：
2.8
通讯作者：
B. Rieger
中科院分区：
文献类型：
--
作者：
Daniel Wendel;W. Eisenreich;C. Jandl;A. Pöthig;B. Rieger
The reaction of the only known room-temperature-stable, acyclic silylsilylene, Si{NDipp(SiMe3)}{Si(SiMe3)3}, toward ethylene was investigated. A full conversion to the silirane product Si{CH2–CH2}{NDipp(SiMe3)}{Si(SiMe3)3} (1) was observed at ambient temperature. However, heating of the benzene solution under an ethylene atmosphere led to an exceptional Si–Si bond insertion to give the modified silirane Si{CH2–CH2}{NDipp(SiMe3)}{CH2–CH2–Si(SiMe3)3} (2a). With respect to the mechanism, an NMR experiment using C2D4 revealed this reaction to proceed via a migratory insertion of the coordinated ethylene of 1 into the Si–Si bond of the ligand framework and subsequent addition of a second ethylene molecule. Moreover, [4+1] cycloaddition with 2,3-dimethyl-1,3-butadiene to give the corresponding silacyclopent-3-ene ring Si{CH2–CH3C═CCH3–CH2}{NDipp(SiMe3)}{Si(SiMe3)3} (3) is reported. All structures were fully characterized by single-crystal X-ray analysis and 1H, 13C, and 29Si NMR spectroscopy.
The reaction of the only known room-temperature-stable, acyclic silylsilylene, Si{NDipp(SiMe3)}{Si(SiMe3)3}, toward ethylene was investigated. A full conversion to the silirane product Si{CH2–CH2}{NDipp(SiMe3)}{Si(SiMe3)3} (1) was observed at ambient temperature. However, heating of the benzene solution under an ethylene atmosphere led to an exceptional Si–Si bond insertion to give the modified silirane Si{CH2–CH2}{NDipp(SiMe3)}{CH2–CH2–Si(SiMe3)3} (2a). With respect to the mechanism, an NMR experiment using C2D4 revealed this reaction to proceed via a migratory insertion of the coordinated ethylene of 1 into the Si–Si bond of the ligand framework and subsequent addition of a second ethylene molecule. Moreover, [4+1] cycloaddition with 2,3-dimethyl-1,3-butadiene to give the corresponding silacyclopent-3-ene ring Si{CH2–CH3C═CCH3–CH2}{NDipp(SiMe3)}{Si(SiMe3)3} (3) is reported. All structures were fully characterized by single-crystal X-ray analysis and 1H, 13C, and 29Si NMR spectroscopy.
影响因子：
2.8
作者：
A. Protchenko;Matthew P. Blake;Andrew D. Schwarz;Cameron Jones;P. Mountford;S. Aldridge
通讯作者：
A. Protchenko;Matthew P. Blake;Andrew D. Schwarz;Cameron Jones;P. Mountford;S. Aldridge