title: 1,3-Diazasilabicyclo[1.1.0]butane with a Long Bridging N-N Bond.
abstract: A 1,3-diazasilabicyclo[1.1.0]butane (1) is synthesized as thermally stable crystals by using the cycloaddition reaction of an isolable dialkylsilylene with aziadamantane. The bridge N-N bond length of 1 (1.70 Å) is the longest among those of known N-N singly-bonded compounds, including side-on bridged transition-metal dinitrogen complexes. The compound 1 is intact in air but moisture sensitive. No reaction occurs with hydrogen, even under pressure at 0.5 MPa. Irradiation of 1 with light gives an isomer quantitatively by N-N and adamantyl C-C bond cleavage. The origin of the remarkable N-N bond elongation is ascribed to significant interaction between a Si-C σ* and Ν-Ν π and σ orbitals as determined by DFT calculations of model compounds.
authors: Hangzhou Normal University, Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, No. 58 Haishu Rd., Hangzhou, 311121, Zhejiang, China.
authors: Xu-Qiong
authors: XQ
authors: Xiao
authors: Hangzhou Normal University, Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, No. 58 Haishu Rd., Hangzhou, 311121, Zhejiang, China.
authors: Zhaowen
authors: Z
authors: Dong
authors: Hangzhou Normal University, Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, No. 58 Haishu Rd., Hangzhou, 311121, Zhejiang, China. zhifanglee@hznu.edu.cn.
authors: Zhifang
authors: Z
authors: Li
authors: Hangzhou Normal University, Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, No. 58 Haishu Rd., Hangzhou, 311121, Zhejiang, China.
authors: Chenting
authors: C
authors: Yan
authors: Hangzhou Normal University, Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, No. 58 Haishu Rd., Hangzhou, 311121, Zhejiang, China.
authors: Guoqiao
authors: G
authors: Lai
authors: Hangzhou Normal University, Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, No. 58 Haishu Rd., Hangzhou, 311121, Zhejiang, China. mkira@m.tohoku.ac.jp.
authors: Mitsuo
authors: M
authors: Kira
keywords: X-ray diffraction; bridging ligands; density-functional calculations; silylene; π interactions