The crystal and molecular structure of chloro-.alpha.,.beta.,.gamma.,.delta.-tetraphenylporphinatomanganese(III)

From activation of dioxygen to formation of high-valent oxo species: Ab initio DFT studies

“…The calculated Mn-Cl bond length is smaller than experimentally measured, which varies between 2.363 and 2.385Å [28,29], and smaller than determined by Zwaans et al (2.553Å) by using HF approach [30]. The discrepancy between the obtained values should be attributed to the fact that LDA often underestimates bond lengths.…”

Structure of chloro(α,β,γ,δ-tetraphenylporphinato)manganese(III) toluene solvate

“…The bond lengths from the Mn atom to the two N atoms distorted further away from the chloro ligands are longer: 2.026 (2) and 2.033 (2)]k compared with 2.000 (2) A. A similar result is seen in the structure of the acetone solvate (Tulinsky & Chen, 1977) though in that case it is of marginal significance. The average Mn--N bond lengths in the two structures are not significantly different.…”

“…During a study of the spectroelectrochemistry of derivatives of Mn In porphyrin complexes, we isolated the title compound and determined its structure. The structure of the complex has been determined previously as the acetone solvate (Tulinsky & Chen, 1977) but the present study is more precise and reveals a number of small but significant diffrrences in the geometry about the Mn atom.…”

Chloro(5,10,15,20-tetraphenylporphyrinato)manganese(III) with 4/m Symmetry

“…These values are smaller than expected for a fivecoordinate Mn m porphyrinate. Indeed, in the crystal structure of [Mn(TPP)CI] as the acetone solvate with no required symmetry for the molecule (Tulinsky &Chen, 1977), an axial Mn--C1 bond distance of 2.363 (3),~, an average Mn--N bond length of 2.008 (15),~ and a Ct...C1 distance of 2.633 A were observed; the Mnatom displacement from the mean plane of the four N atoms was 0.27 .~. Essentially identical values were obtained for the chloroform solvate of [Mn(TPP)CI] (Hoard, 1975).…”