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Theoretical Chemistry Accounts

, Volume 107, Issue 6, pp 336–342 | Cite as

Density functional computation of 55Mn NMR parameters

  • Michael Bühl
Regular article

Abstract.

Gradient-corrected (GGA) and hybrid variants of density functional theory are used to compute geometries and 55Mn chemical shifts of MnO4, Mn(CO)6+, Mn2(CO)10, Mn(CO)5X [X=H, Cl, C(O)Me], Mn(CO)5, Mn(NO)3(CO), and Mn(C5H5)L x [L x =(CO)3, C6H6, C7H8]. For this set of compounds, substituent effects on δ(55Mn) are significantly underestimated with the pure GGA functional BPW91 and are well described with hybrid functionals such as mPW1PW91 and, in particular, B3LYP. The computed data provide evidence for solvent and counterion effects on δ(55Mn) of MnO4 and Mn(CO)6+, respectively. The latter, in the presence of Cl, may be described as highly fluxional Mn(CO)5C(O)Cl. Electric field gradients computed with the B3LYP functional can be used for a qualitative rationalization of observed trends in 55Mn NMR line widths. Electronic supplementary material to this paper can be obtained by using the Springer LINK server located at http://dx.doi.org/10.1007/s002140020338x

Key words:55Mn NMR – Density functional calculations – Chemical shift computations – Electric field gradients – NMR line widths 

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Copyright information

© Springer-Verlag Berlin Heidelberg 2002

Authors and Affiliations

  • Michael Bühl
    • 1
  1. 1.Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr, Germany e-mail: buehl@mpi-muelheim.mpg.deDE

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