A theoretical study on the structure and nature of the Mn-X bond in tetraphenylporphyrin and its manganoporphyrines containing halogen as an axial ligand [Mn(TPP)X] {X=F, Cl and Br} was carried through density functional B3LYP/6-311G and M06/def2TZVP methods. Comparison of length and angle of bonds in the optimized geometry of [Mn(TPP)Cl] to its X-ray single crystal structure revealed that M06/def2TZVP basis set resulted in more realistic outcomes. Furthermore, the Mn–X bond was analyzed using AIM and NBO to obtain its nature and order in the presence of different halogen axial ligands. The results showed that the Mn-X bond has a σ nature with no π-back donation from Mn to X ligand and the bond order decreased from F to Br. In addition, the effect of axial ligands on the global and local chemical reactivity descriptors of manganoporphyrins has been discussed.

通过密度泛函B3LYP / 6-对四苯基卟啉及其以卤素为轴向配体[Mn（TPP）X] {X = F，Cl和Br}的锰卟啉中Mn-X键的结构和性质进行了理论研究。 311G和M06 / def2TZVP方法。比较[Mn（TPP）Cl]的最佳几何构型与其X射线单晶结构的键长和键角，发现M06 / def2TZVP基组可产生更实际的结果。此外，使用AIM和NBO对Mn–X键进行了分析，以在不同的卤素轴向配体存在下获得其性质和顺序。结果表明，Mn-X键具有σ性质，从Mn到X配体无π-返给，键序从F到Br降低。此外，