Acta Scientiarum Naturalium Universitatis Pekinensis

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Theoretical Studies on the IR Spectra of Co2(CO)8 and the Catalytic Activities of HCo(CO)3 and HCo(CO)4

HOU Ruobing1,YI Xianghui2,LU Danmei3   

  1. 1Department of Chemistry, Guangxi Normal Un iversity, Guilin, 541004; 2Department of Resource and Environmental Sciences, Guangxi Normal University, Guilin, 541004; 3Department of Science and Engineering, Guangxi Radio and TV University, Nanning, 530022
  • Received:2001-12-12 Online:2002-11-20 Published:2002-11-20



  1. 1广西师范大学化学系,桂林,541004;2广西师范大 学资源与环境学系,桂林,541004;3广西广播电视大学理工部,南宁,530022

Abstract: Studies on the band positions in IR spectra of Co2(CO)8 with the C2v symmetry and the catalytic activities of the species, HCo(CO)3 and HCo(CO)4,in the reaction of the olefin hydroformylation have been carried out by using quantum chemical calculation at the B3LYP/6-3 1G* level. Two structures of the Co2(CO)8, the geometry of C2v symmetry, as well as the conformation of D3d symmetry, have been optimized and the structure optimized of C2v symmetry Co2(CO)8 agrees well with experimental structure and is 28.80kJ/mol more stable than D3d one. The band pos itions in IR spectra of C2v symmetry Co2(CO)8 is well in accord with the experimental studies. It is found that the active catalytic species, HCo(CO)3 and HCo(CO)4, have C2v and C3vsymmetries, respectively, and that the catalytic activity of HCo(CO)3 is better than HCo(CO)4. In addition, the π bond between ethene and HCo(CO)3 has been formed in the coordinate catalytic reaction and the theoretical bond energy is 100.80kJ/mol.

Key words: Octacarbonyldicobalt, HCo(CO)3, HCo(CO)4, electronic structure, IR spectra, catalytic activity

摘要: 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28.80kJ/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100.80kJ/mol。

关键词: 八羰基合二钴, 三羰基一氢合钴, 四羰基一氢合钴, 电子结构, 红外光谱, 催化活性

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