Structural and electron density studies on a chromium(IV)-oxo complex [CrIV(O)(TMP)]

Abstract

The electron density distribution of a chromium(IV)-oxo complex, [CrIV(O)(TMP)] (TMP = 5,10,15,20-tetrakis-p-methoxyphenyl porphyrin), is investigated by molecular orbital calculation. The molecular and crystal structure of the compound is studied by x-ray diffraction. It belongs to the space group I 2, Z = 2, a = 14.979(4) Å, b = 9.752(3), c = 15.605(3) Å, β = 100.97(2)°, V = 2238(1) Å3, Mo Kα radiation λ = 0.7107 Å, R = 4.9%, Rw = 3.5% for 3575 observed reflections. Cr is five-coordinated in a square pyramidal fashion with the Cr atom located 0.42 Å toward the oxo-ligand. Deformation density maps are derived from the single point molecular orbital calculation on the basis of HF and DFT(density functional theory) calculations. The accumulation of deformation density along the C-H, C-C, C-N and C-O bonds in the porphyrin ligand is well represented. The asphericity in electron density around the Cr ion is clearly demonstrated. Natural bond orbital analysis (NBO) reveals that the Cr-Ooxo is actually a triple-bond character (σ2π4) and the four N of pyrrole serves as a σ-donor to Cr. The Cr-Npyrrole bond is essentially a dative bond. d-Orbital populations of Cr derived from both calculations are in good agreement with each other. Planar dπ-orbital is the most populated, which is in accord with the prediction from crystal field theory. Detail bond characterization of the Cr-L, multiple bond is discussed.