Abstract
The conformational preferences of the axial ligands have been determined for several metalloporphyrins MPL and MPLL′ (M = Mo, Fe; P = porphine dianion; L and L′ being the axial ligands). For MoP(C2H2) a qualitative analysis indicates that the conformation with the acetylenic bond eclipsing two Mo-N bonds will be favored. Ab initio SCF calculations indicate that:
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(i)
iron porphyrins with an axial imidazole ligand show a flat potential energy curve for the rotation of the imidazole ligand;
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(ii)
iron porphyrins with a dioxygen ligand prefer the staggered conformation with the O-O bond projecting along the bisectors of the Fe-N bonds;
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(iii)
in the cis-dinitrosyl molybdenum porphyrin, the nitrosyl ligands should be eclipsed with respect to the Mo-Npyr bonds.
These theoretical predictions are compared with the experimental structures from the literature.
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Rohmer, MM., Strich, A. & Veillard, A. Conformational preferences of the axial ligands in some metalloporphyrins. A theoretical study. Theoret. Chim. Acta 65, 219–231 (1984). https://doi.org/10.1007/BF00551335
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DOI: https://doi.org/10.1007/BF00551335