Theoretical study on ligand exchange reaction mechanisms of iron(IV) complexes with two different group 14 element ligands, Cp(CO)FeH(EEt3)(E′Et3) with (HEEt3) (E, E′ = Si, Ge, Sn)

A computational study with Becke3LYP of DFT was carried out to investigate the ligand exchange reaction mechanisms of Cp(CO)FeH(EEt3)(E′Et3) with (HEEt3) (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 HEEt3 from the Fe(IV) center takes place more readily in the order Et3Si–H > Et3Ge–H ≫ Et3Sn–H. There are several reasons for the order: (i) the thermodynamic stability of the corresponding products, (ii) the order of bond binding energy: Et3Si–H > Et3Ge–H > Et3Sn–H, (iii) the order of the interaction of E–H: Et3Si–H > Et3Ge–H > Et3Sn–H.