Intramolecular hydrogen bonding interaction, a mechanism for the bridging linkages to exert electronic influence on diiron models of ”FeFe”-hydrogenase
Seven diiron hexacarbonyl complexes,”Fe2(L)(CO)6” (L =two monothiolate or dithiolate ligans),as the mimics of the diiron subunit of ”FeFe”-hydrogenase were theoretically investigated using density functional theory (DFT) to examine the electronic influences of the bridging linkages of the complexes on their electrochemical behaviours.In the calculations,the energies and the compositions of the frontier orbitals of these complexes were estimated.Charge distributions of the complexes were calculated using natural population analysis (NPA).The influence of the functional groups of the bridging linkages on the diiron core via intrarnolecular hydrogen interactions was explored using topological analysis.The results indicated that the bridging linkages of the complexes affect significantly the compositions of the HOMOs whereas hardly alter the compositions of the LUMOs.The correlations of the energies of the frontier orbitals to the redox potentials of the examined complexes were also discussed.
Density functional theory (DFT) diiron-carbonyl complexes electrochemistry ”FeFe”-hydrogenase intramolecular hydrogen-bonding
Hailong Wang Xiaoming Liu
College of Biological, Chemical Sciences and Engineering Jiaxing University, Jiaxing 314001,China
国内会议
开封
英文
110-110
2012-07-02（万方平台首次上网日期，不代表论文的发表时间）