论文部分内容阅读
在B3LYP 6 31G 水平上对Co2 (CO) 8红外光谱及烯烃氢甲酰化催化反应的催化活性中间体HCo(CO) 4和HCo(CO) 3 的结构进行了优化及相关计算 ,结果表明 :( 1)Co2 (CO) 8的两种稳定构象态分别具有C2v和D3d对称性 ,计算所得的结构数据与实验值具有极好的一致性。C2v对称性的Co2 (CO) 8比D3d对称性的Co2 (CO) 8的能量低 2 8 80kJ mol;( 2 )C2v对称性的Co2 (CO) 8的红外吸收峰的计算结果与实验值极为接近 ;( 3)催化反应的活性中间体HCo(CO) 4和HCo(CO) 3 的稳定构象态分别具有C3v和C2v对称性 ,其中HCo(CO) 3 比HCo(CO) 4具有更高的催化活性 ;( 4 )催化反应中乙烯与HCo(CO) 3 形成了相对稳定的π配合物 ,该配合物中π配键的键能约为 10 0 80kJ mol。
The structures of the catalytic active intermediates HCo (CO) 4 and HCo (CO) 3 of Co2 (CO) 8 and the olefinic hydroformylation catalyzed reactions were optimized and correlated at B3LYP 6 31G level. The results showed that: (1) The two stable conformational states of Co2 (CO) 8 have C2v and D3d symmetry, respectively, and the calculated structural data are in good agreement with the experimental data. The C2v symmetry Co2 (CO) 8 is 2880kJ mol lower than that of D3d symmetry Co2 (CO) 8. (2) The calculation results and experimental results of the C2v symmetry Co2 (CO) (3) The stable conformational states of the active intermediates HCo (CO) 4 and HCo (CO) 3 of the catalytic reaction have the symmetry of C3v and C2v, respectively, and HCo (CO) 3 has a higher (4) In the catalytic reaction, ethylene and HCo (CO) 3 form a relatively stable π complex. The bond energy of the π bond in this complex is about 10 0 80 kJ mol.