NMR spectroscopy of a 18O-labeled rhodium paddlewheel complex: Isotope shifts, 103Rh–103Rh spin–spin coupling, and 103Rh singlet NMR

Author:

Harbor-Collins Harry1ORCID,Sabba Mohamed1,Bengs Christian1ORCID,Moustafa Gamal1,Leutzsch Markus2ORCID,Levitt Malcolm H.1ORCID

Affiliation:

1. School of Chemistry, University of Southampton 1 , Southampton SO17 1BJ, United Kingdom

2. Max-Planck-Institut für Kohlenforschung 2 , Kaiser-Wilhelm-Platz 1, Mülheim an der Ruhr 45470, Germany

Abstract

Despite the importance of rhodium complexes in catalysis, and the favorable 100% natural abundance of the spin-1/2 103Rh nucleus, there are few reports of 103Rh nuclear magnetic resonance (NMR) parameters in the literature. In part, this is the consequence of the very low gyromagnetic ratio of 103Rh and its dismal NMR sensitivity. In a previous paper [Harbor-Collins et al., J. Chem. Phys. 159, 104 307 (2023)], we demonstrated an NMR methodology for 1H-enhanced 103Rh NMR and demonstrated an application to the 103Rh NMR of the dirhodium formate paddlewheel complex. In this paper, we employ selective 18O labeling to break the magnetic equivalence of the 103Rh spin pair of dirhodium formate. This allows the estimation of the 103Rh–103Rh spin–spin coupling and provides access to the 103Rh singlet state. We present the first measurement of a 18O-induced 103Rh secondary isotope shift as well as the first instance of singlet order generated in a 103Rh spin pair. The field-dependence of 103Rh singlet relaxation is measured by field-cycling NMR experiments.

Funder

HORIZON EUROPE European Research Council

Engineering and Physical Sciences Research Council

Publisher

AIP Publishing

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