Chatterjee Arpita, Mondal Sonjoy, Saha Rohini, Pal Poulami, Chakrabarty Kuheli, Das Gourab Kanti
Department of Chemistry, Visva-Bharati, Santiniketan 731235 West Bengal, India.
ACS Omega. 2018 Nov 28;3(11):16165-16174. doi: 10.1021/acsomega.8b02344. eCollection 2018 Nov 30.
In this paper, the mechanistic studies on the isomerization of hydroxyl and silyl derivatives of bicyclic cyclopropanes under the catalytic action of Zeise's salt have been reported. The catalytic activity of both the monomeric and the dimeric forms of Zeise's salt has been studied by applying the high-level quantum mechanical method. Results from this investigation reveal that the reaction goes favorably under the catalysis of the dimeric form of Zeise's salt. The calculated activation barrier for the catalytic process using Zeise's dimer reveals that the rearrangement occurs with an activation barrier of 19-25 kcal mol. Depending on the nature of substituents present on the substrate, formation of various products has been explained. This study also includes the heteronuclear counter part of Zeise's dimer where one of the Pt-metals is replaced by palladium (Pd) and nickel (Ni) successively. The calculated activation barrier using these heteronuclear catalysts is found to be close enough to that calculated for the catalytic pathway using Zeise's dimer.
本文报道了在蔡氏盐催化作用下双环环丙烷的羟基和硅烷基衍生物异构化的机理研究。采用高水平量子力学方法研究了蔡氏盐单体和二聚体形式的催化活性。该研究结果表明，在蔡氏盐二聚体的催化作用下，反应顺利进行。使用蔡氏二聚体计算的催化过程活化能垒表明，重排反应的活化能垒为19 - 25 kcal/mol。根据底物上取代基的性质，解释了各种产物的形成。该研究还包括蔡氏二聚体的异核类似物，其中Pt金属之一依次被钯（Pd）和镍（Ni）取代。发现使用这些异核催化剂计算的活化能垒与使用蔡氏二聚体计算的催化途径的活化能垒足够接近。
