摘要
以Ni+与C3H8反应作为过渡金属离子与烷烃反应的范例体系,用B3LYP密度泛函方法计算了[Ni,C3,H8]+基态势能面上各驻点的构型、频率和能量,结果表明,该反应的H2分子消除需经历两个基元步骤,即Ni+ 首先插入一级或二级C- H键,然后经H转移过渡态异构化为较稳定的中间体,继而解离产生H2 分子.计算的反应热为 142.28 kJ/mol,与相应的实验值(127.85 kJ/mol)符合较好.
Abstract The reaction of Ni+ with propane have been studied extensively by using density functional theory , and the detailed information regarding the mechanism and energetics of H2 elimination on the potential energy surface of [Ni,C3,H8]+ have been obtained at B3LYP/6-311 + +G(3df/,3pd) level. Both the initial primary or secondary C桯 bond activations in propane mediated by Ni+ in the reaction of Ni+ with propane can result in the H2 elimination from Ni(C3H8) + . Five intermediates, two C桯 bond activation transition states and three H-shift transition states are located on this potential energy surface. The heat ofreaction for Ni++C3H8 Ni(C3H6)++H2 is calculated to be 142. 28 kj/mol. This result is in goodagreement with the experimental finding, a value of 127. 85 kJ/mol at 0 K.
出处
《高等学校化学学报》
SCIE
EI
CAS
CSCD
北大核心
2002年第5期876-879,共4页
Chemical Journal of Chinese Universities
基金
山东省自然科学基金重大项目(批准号:Z2000B02)资助.