取代基对有机铬化合物分子内氢转移反应势垒的影响(英文)

Effect of Substituent on the Reaction Barrier of Intramolecular α-hydrogen Transfer from Alkyl to Alkylidyne Ligand in Organochromium Complexes

使用密度泛函理论B3LYP方法研究了取代基对一系列有机Cr化合物(R3)(R4)Cr(≡CH)(CHR1R2)分子内α-H转移反应能垒的影响。确定了反应物、过渡态和产物的几何结构和反应势垒。研究结果表明,当R1和R2是甲基,R3和R4是PH2基团、Silyl基团或Cl原子时,反应势垒最低。

Density functional theory B3LYP method is carried out to investigate the effect of substituent on the reaction barrier of intramolecular α-hydrogen transfer from alkyl to alkylidyne ligands in a series of organometallic chromium complexes （R3）（R4）Cr（≡CH）（CHR1R2）. The optimal structures of reactants, transition states and products are obtained. The reaction barriers are then estimated. Calculation results indicate that the most preferable substituent is a methyl group for R1 and/or R2. For R3 and/or R4, the favorite substituent is a PH2 group or a silyl group or a chlorine atom.