Summary
The novel theoretical scheme IMOMM, integrating ab initio and molecular mechanics contributions in a single geometry optimization process, is applied to the structural determination of different [OsO4(NR3)] (NR3 = bulky chiral alkaloid derivative) species closely related to active catalysts for the asymmetric dihydroxylation of olefins. Computed values compare in a satisfactory way with available X-ray data, the relationship between the Os-N distance and the nature of the NR3, ligand being properly reproduced. The computational scheme allows the separate quantification of electronic and steric effects, as well as the identification of the specific steric repulsions responsible for the difference.
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Apart from the modifications required by the method [8], all torsional contributions associated to dihedral angles involving the metal atom were set to zero. Finally, the very few parameters of complex 2 that are not provided by the program were set to values corresponding to similar atoms
In the ab initio calculation, the N-H distances were frozen to 1.015 Å. In the molecular mechanics calculation, the corresponding N-C distances were frozen to their experimental value in the X-ray structure of 2
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Ujaque, G., Maseras, F. & Lledós, A. A theoretical evaluation of steric and electronic effects on the structure of [OSO4 (NR3)] (NR3 = bulky chiral alkaloid derivative) complexes. Theoret. Chim. Acta 94, 67–73 (1996). https://doi.org/10.1007/BF00194932
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DOI: https://doi.org/10.1007/BF00194932