Observability of Paramagnetic NMR Signals at over 10 000 Ppm Chemical Shifts

Overview

Journal Angew Chem Int Ed Engl

Specialty Chemistry

Date 2021 Aug 5

PMID 34351041

Citations 7

Authors

Jonas C Ott

Elizaveta A Suturina

Ilya Kuprov

Joscha Nehrkorn

Alexander Schnegg

Markus Enders

Lutz H Gade

Affiliations

Soon will be listed here.

Abstract

We report an experimental observation of P NMR resonances shifted by over 10 000 ppm (meaning percent range, and a new record for solutions), and similar H chemical shifts, in an intermediate-spin square planar ferrous complex [ (PNP)Fe-H], where PNP is a carbazole-based pincer ligand. Using a combination of electronic structure theory, nuclear magnetic resonance, magnetometry, and terahertz electron paramagnetic resonance, the influence of magnetic anisotropy and zero-field splitting on the paramagnetic shift and relaxation enhancement is investigated. Detailed spin dynamics simulations indicate that, even with relatively slow electron spin relaxation (T ≈10 s), it remains possible to observe NMR signals of directly metal-bonded atoms because pronounced rhombicity in the electron zero-field splitting reduces nuclear paramagnetic relaxation enhancement.

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