Theoretical study on ligand exchange reaction mechanisms of iron(IV) complexes with two different group 14 element ligands, Cp(CO)FeH(EEt _3)(E′Et_3) with (HEEt_3) (E, E′ = Si, Ge, Sn)

摘要

A computational study with Becke3LYP of DFT was carried out to investigate the ligand exchange reaction mechanisms of Cp(CO)FeH(EEt_3) (E′Et_3) with (HEEt_3) (E, E′ = Si, Ge, Sn). The full ligand exchange reactions were computed, starting from the reductive elimination and then followed by the oxidative addition. The reductive elimination of HEEt_3 from the Fe(IV) center takes place more readily in the order Et_3Si-H > Et_3Ge-H ? Et_3Sn-H. There are several reasons for the order: (i) the thermodynamic stability of the corresponding products, (ii) the order of bond binding energy: Et _3Si-H > Et_3Ge-H > Et_3Sn-H, (iii) the order of the interaction of E-H: Et_3Si-H > Et_3Ge-H > Et_3Sn-H.