TY - DATA T1 - Theoretical investigation of different reactivities of Fe(IV)O and Ru(IV)O complexes with the same ligand topology PY - 2016/12/26 AU - Zhe Tang AU - Yi Wang AU - Peng Zhang UR - https://tandf.figshare.com/articles/journal_contribution/Theoretical_investigation_of_different_reactivities_of_Fe_IV_O_and_Ru_IV_O_complexes_with_the_same_ligand_topology/4496960 DO - 10.6084/m9.figshare.4496960.v1 L4 - https://ndownloader.figshare.com/files/7266494 KW - Non-heme KW - density functional theory calculation KW - hydrogen abstraction KW - topology effect N2 - The structures and mechanisms for hydrogen abstraction from isopropylbenzene for four high-valence complexes, cis-β-[FeIV(O)(BQCN)]2+ (Fe-2b and Fe-2b-2) and cis-β-[RuIV(O)(BQCN)]2+ (Ru-2b and Ru-2b-2) (BQCN = N,N′-dimethyl-N,N′-bis(8-quinolyl)-cyclohexanediamine), were investigated using density functional theory. Of the two iron complexes, Fe-2b-2 has more exposed FeO units than Fe-2b, with iron being further out of the equatorial plane because of the steric interaction of the same ligand topologies with the iron-oxo group trans to a quinolyl or amine nitrogen. The contribution of BQCN to Fe-2b is higher than the contribution to Fe-2b-2 as shown by the density-of-states spectra. The iron isomers can abstract hydrogen from isopropylbenzene via two-state reactivity patterns, whereas the ruthenium isomers react with isopropylbenzene via a single-state mechanism. In the gas phase, the relative reactivity exhibits the trend Fe-2b > Fe-2b-2, whereas with the addition of the ZPE correction and the SMD model, the relative reactivity follows Fe-2b-2 > Fe-2b. For the ruthenium complexes, the relative reactivity follows the trend Ru-2b-2 > Ru-2b in both the gas phase and solvent. Thus, the same ligand topologies with the metal-oxo group trans to a different nitrogen affect the reactivities of the iron and ruthenium complexes. ER -