【摘要】 采用密度泛函理论B3LYP方法,对两类金（I）配合物AuX（X=F,CI,Br,I）和AuPR₃⁺（R=F,CI,Br,I,H,Me,Ph）.催化C₂H₄加氢反应的机理进行了理论研究.计算显示Au（I）配合物对C₂H₄氢化具有较好的催化效果,其作用下的加氢反应存在"活化H—H键后再与C₂H₄反应"和"活化C=C键后再与H₂反应"两种途径,前者的活化能较后者低90-120 kJ·mol^-1,因而具有明显的能量优势.研究表明AuPR_3⁺的催化能力明显强于AuX.此外,X/PR₃基团供、吸电子能力的变化对配合物的催化能力也具有较为显著的影响.电子结构分析显示Au（I）配合物在C₂H₄加氢反应中不仪能够削弱H—H、C=C键的强度,还使H₂σ_H-H^*、C₂H₄π_C-C^*轨道能级下降,从而缩小了π_c=c-σ_H-H^*或σ_H-H-π_C=C^*轨道间的能级差,促进了C-2H₄-H₂反应中的电子离域,从而降低禁阻反应发生的难度.σ_H-H^*、π_C=C^*轨道能级改变量与加氢反应活化能E_a的降低值之间存在较好的一致性关系,因此使上述轨道能级下降幅度越大的Au（I）配合物可以获得较好的催化效果.更多还原

【Abstract】 The reaction mechanisms of ethylene hydrogenation catalyzed by Au（l） complexes AuX（X=F, CI,Br,I） and AuPRJ（R = F,CI,Br,I,H,Me,Ph） were investigated using density functional theory at the B3LYP level.The calculated results indicated that Au（l） complexes were effective catalysts in the hydrogenation of ethylene.AuPRS showed higher catalytic activity than AuX and the effect of changing the electron donating or withdrawing ability of the ligand on catalytic activity was large.Natural bond orbital analysis indicated that the interactions between the Au（l） complex and H₂/C₂H₄ not only weakened the H-H/C =C bond strength,but also decreased the energy of theσ_H-H^*、π_C=C^* orbital level.As a result,the energy differences ofπ_C=C-σ_H-H^*/σ_H-H-π_C=C^* decreased,and ethylene hydrogenation was facilitated.A linear correlation was observed between the activation energies andπ_C=C-σ_H-H^*/σ_H-H-π_C=C^*.The more an Au（l） complex affected theσ_H-H^*/π_C=C^* orbital levels,the higher its catalytic activity.更多还原