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Updated: Jun 1, 2026

Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex
Published on: July 27, 2022
Secondary coordination sphere interactions facilitate the insertion step in an iridium(III) CO2 reduction catalyst
Timothy J Schmeier1, Graham E Dobereiner, Robert H Crabtree
1The Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 06520, USA.
Abstract:
There is considerable interest in both catalysts for CO(2) conversion and understanding how CO(2) reacts with transition metal complexes. Here we develop a simple model for predicting the thermodynamic favorability of CO(2) insertion into Ir(III) hydrides. In general this reaction is unfavorable; however, we demonstrate that with a hydrogen bond donor in the secondary coordination sphere it is possible to isolate a formate product from this reaction. Furthermore, our CO(2) inserted product is one of the most active water-soluble catalysts reported to date for CO(2) hydrogenation.
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