The effects of axial ligand on the oxygen atom transfer(OAT)reaction from 5,10,15-tris(pentafluorophenyl)corrole((tpfc)MnVO)to dimethyl sulfide(DMS)have been investigated by density functional theory(DFT)calculations.Imidazole(Im),4-methylimidazole(4-MI)and pyridine(Py)were selected as the axial ligands.The results revealed that the axial ligand can form coordinate bond with(tpfc)MnVO in the transition state(TS)of the OAT reaction.The axial coordination favored charge transferring from(tpfc)MnVO to DMS,and weakened the Mn≡O bond in both singlet and triplet states.Furthermore,axial coordination can reduce the energy barrier of neutral(tpfc)MnVO from 23.62 kJ·mol^-1 to less than 3 kJ·mol^-1 in the triplet state,which is significantly lower than in the singlet state.This makes(tpfc)MnVO tend to direct the OAT reaction via triplet state pathway.On the other hand,the energy barriers of[(tpfc)MnVIO]+species from disproportionation pathway increased from 1.26 to 33.95 kJ·mol^-1 in a doublet state.This suggests axial ligands were conducive for direct(tpfc)MnVO OAT reaction pathway.
Density functional theory at the BP86 level was used to investigate the influence of equatorial ligands on the Ni–Ni interactions and magnetic coupling properties of metal string complexes [Ni3（L）4（NCS）2] （L represents the rigid equatorial ligands; L = dzp- （1）, mpmpa- （2）, mppda- （3）, mptpa- （4））. The following conclusions can be drawn. （1） With increasing the radius of the connecting atom in the cental ring in equatorial ligands, the two pyridine rings bend down, resulting in the decreasing distance between the two pyridine-nitrogen atoms and the Ni–Ni distance. Therefore, the strength order of the Ni–Ni interaction is 4 〉 2 〉 3 〉 1. The Ni–Ni interactions in 2 and 4 are stronger than those in Ni3（dpa）4（NCS）2 containing no-rigid equatorial ligands. （2） The calculated -Jab is 4 〉 2 〉 3 〉 1. There are two types of magnetic exchange pathways in these complexes： the σ-type pathway through the Ni36＋ chains and the δ-type pathway through the equatorial ligands. The magnetic coupling through the metals is the dominant part. Hence, the magnetic coupling strength increases with increasing the Ni–Ni interaction. Modifying the radius of the connecting atom may be one of the means to fine tuning of magnetic coupling strength of this kind of metal string complexes.
