Le probleme de la conjugaison a travers un atome de silicium π-lie dans les systemes sila-2 butadieniques
作者:G. Bertrand、G. Manuel、P. Mazerolles、G. Trinquier
DOI:10.1016/s0040-4020(01)92358-0
日期:1981.1
values Two mechanisms can explain the nature of the products obtained on the co-thermolysis of the cyclic compounds with phenol, one with 1-silacyclobut-1-ene intermediate and the other involving an allylic silicenium cation. In both hypothetical mechanisms, the 2-silabutadienes behave as a conjugated system since they lead either to (2+2) cycloaddition or to (1,2)- and (1,4)-electrophilic addition. This
针对不同pKa值的羟基化化合物,研究了通过热解或光解各种1-乙烯基硅环环丁烷而作为瞬时中间体形成的sila-2丁二烯的化学行为。两种机理可以解释在共聚条件下获得的产物的性质。用苯酚对环状化合物进行热解,一种用1-silacyclobut-1-ene中间体进行热解,另一种用烯丙基硅鎓阳离子进行热解。在这两种假设的机制中,2-silabutadienes表现为共轭体系,因为它们导致(2 + 2)环加成或导致(1,2)-和(1,4)亲电子加成。通过丁二烯和2-硅丁二烯的离域能的计算支持了通过硅原子发生共轭现象的证据。