Access to a Stable Si2N2Four-Membered Ring with Non-Kekulé Singlet Biradical Character from a Disilyne,Journal of the American Chemical Society

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Access to a Stable Si2N2Four-Membered Ring with Non-Kekulé Singlet Biradical Character from a Disilyne
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2011-08-17 , DOI: 10.1021/ja2059846
Katsuhiko Takeuchi ₁ , Masaaki Ichinohe ₁ , Akira Sekiguchi ₁

Affiliation

The reactions of 1,1,4,4-tetrakis[bis(trimethylsilyl)methyl]-1,4-diisopropyltetrasila-2-yne 1 with an equivalent amount of trans- and cis-3,3',5,5'-tetramethylazobenzenes produced a Si(2)N(2) four-membered ring biradicaloid [RSi(μ-NAr)(2)SiR] 2 (R = Si(i)Pr[CH(SiMe(3))(2)](2), Ar = 3,5-Me(2)C(6)H(3)), which was isolated as air- and moisture-sensitive dark purple crystals. Compound 2 displays no EPR signal, and the molecular structure of 2 was characterized by NMR spectroscopy and X-ray crystallography, revealing that 2 has a planar centrosymmetric Si(2)N(2) four-membered ring. The Si1-Si1' distance is 2.63380(9) Å, and there is no bond interaction between the Si1 and Si1' atoms of 2. The reactions of 2 with methanol and carbon tetrachloride show that 2 has both closed-shell and radical-type reactivity.

中文翻译：

从二甲硅烷获得具有非凯库勒单线态双自由基的稳定 Si2N2 四元环

1,1,4,4-四[双（三甲基甲硅烷基）甲基]-1,4-二异丙基四硅-2-炔 1 与等量的反式和顺式-3,3',5,5'-的反应四甲基偶氮苯产生 Si(2)N(2) 四元环双自由基 [RSi(μ-NAr)(2)SiR] 2 (R = Si(i)Pr[CH(SiMe(3))(2)]( 2), Ar = 3,5-Me(2)C(6)H(3))，分离为对空气和水分敏感的深紫色晶体。化合物 2 显示没有 EPR 信号，2 的分子结构的特点是核磁共振波谱和 X 射线晶体学，揭示 2 具有平面中心对称 Si(2)N(2) 四元环。Si1-Si1'距离为2.63380(9) Å，2的Si1和Si1'原子之间没有键相互作用。2与甲醇和四氯化碳的反应表明2具有闭壳型和自由基型反应性。

更新日期：2011-08-17

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