Kohn–Sham calculations of NMR shifts for paramagnetic 3d metal complexes: protocols, delocalization error, and the curious amide proton shifts of a high-spin iron(ii) macrocycle complex

Author:

Martin Bob12345ORCID,Autschbach Jochen12345

Affiliation:

1. Department of Chemistry

2. University at Buffalo

3. State University of New York

4. Buffalo

5. USA

Abstract

Ligand chemical shifts (pNMR shifts) are analyzed using DFT. A large difference in the amide proton shifts of a high-spin Fe(ii) complex arises from O → Fe dative bonding which only transfers β spin density to the metal.

Funder

U.S. Department of Energy

Publisher

Royal Society of Chemistry (RSC)

Subject

Physical and Theoretical Chemistry,General Physics and Astronomy

Reference104 articles.

1. S. Moon and S.Patchkovskii, First–principles calculations of paramagnetic NMR shifts, in Calculation of NMR and EPR Parameters. Theory and Applications, ed. M. Kaupp, M. Bühl and V. G. Malkin, Wiley-VCH, Weinheim, 2004, pp. 325–338

2. J. Autschbach , NMR Calculations for Paramagnetic Molecules and Metal Complexes, in Annual Reports in Computational Chemistry, ed. D. A. Dixon, Elsevier, Amsterdam, 2015, vol. 11, pp. 3–36

3. Modeling EPR parameters of nitrogen containing conjugated radical cations

4. Characterization of Paramagnetic Reactive Intermediates: Predicting the NMR Spectra of Iron(IV)-Oxo Complexes by DFT

5. Predicting the spin state of paramagnetic iron complexes by DFT calculation of proton NMR spectra

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