A C2-Linked Bis-silene Formed without Using Metals and the Transformation into the Bis-silyl and Bis-silylium C4-Cumulenes

被引:10
作者
Chen, Yilin [1 ]
Li, Jiancheng [1 ]
Jiang, Wenjun [1 ]
Zhao, Jinbo [1 ]
Zhu, Hongping [1 ]
Muhammed, Shahila [2 ]
Parameswaran, Pattiyil [2 ]
Roesky, Herbert W. [3 ]
机构
[1] Xiamen Univ, Coll Chem & Chem Engn, State Key Lab Phys Chem Solid Surfaces, Natl Engn Lab Green Chem Prod Alcohols Ethers Est, Xiamen 361005, Peoples R China
[2] Natl Inst Technol Calicut, Kozhikode 673601, Kerala, India
[3] Georg August Univ, Inst Anorgan Chem, D-37077 Gottingen, Germany
关键词
X-RAY; ACCESS; REACTIVITY; CUMULENE; SILICON;
D O I
10.1021/acs.organomet.0c00368
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Reaction of silylene L(Cl)Si: (1; L = PhC(NtBu)(2)) with 1,3-diyne Me3SiC equivalent to CC equivalent to CSiMe3 produced bis-silene L(Cl)Si-C(SiMe3)C equivalent to C(SiMe3)C-Si(Cl)L (2). This shows a route by oxidative coupling reaction to silenes. Reaction of 2 with AgOSO2CF3 resulted in [L(Cl)(F3CO2SO)Si](Me3Si)C=C=C=C(SiMe3)[Si(OSO2CF3)(Cl)L] (3) and a silver mirror. From the reaction of 2 and B(C6F5)(3) were isolated compounds {[L(Cl)Si](Me3Si)C=C=C=C(SiMe3)[Si(Cl)L]}(2+)center dot 2[ClB(C6F5)(3)](-) (4) and {LSi[mu(2)-C-2(SiMe3)(C equivalent to CSiMe3)]}(2) (5). When 2 was treated with [Ph3C](+)[B(C6F5)(4)](-), compounds [L-2(Cl)Si](+)[B(C6F5)(4)](-) (6) and Ph2C=-cyclo-C(CH-CH)(2)CHCPh3 (7) were formed. These reactions exhibit reduction of the polar Si-C bond to create unusual species of neutral and dicationic C-4-cumulenes. The formation, bonding, and reactivity of compound 2 is explored by the computational quantum mechanical calculations.
引用
收藏
页码:4282 / 4286
页数:5
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