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Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex
Published on: July 27, 2022
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Protonation-Induced Electron Density Redistribution Facilitates Aggregation in PNNP Dicopper Hydride Complexes
Roel Laurentius Maria Bienenmann1, Chattawat Thangsrikeattigun2,3, Alexandra Julia Schanz1
1Organic Chemistry and Catalysis, Institute For Sustainable and Circular Chemistry, Utrecht University, Utrecht, Netherlands.
Chemistry (Weinheim an Der Bergstrasse, Germany)
|December 16, 2025
Summary
Ligand protonation and charge influence copper hydride complex aggregation. Protonation favors dimerization by altering electronic structure, while charge disfavors it by reducing electrostatic stabilization.
Area of Science:
- Inorganic Chemistry
- Organometallic Chemistry
- Materials Science
Background:
- Copper(I) hydride complexes display varied aggregation, impacting reactivity and structure.
- Pincer ligands, like PNNP, are crucial in stabilizing metal complexes.
Purpose of the Study:
- Investigate aggregation behavior in dicopper hydride complexes with PNNP ligands.
- Correlate aggregation with ligand protonation state and electronic factors.
- Identify key determinants of aggregation in these systems.
Main Methods:
- Combined experimental and computational approaches.
- Synthesis and characterization of dicopper hydride complexes.
- Density Functional Theory (DFT) calculations.
Main Results:
- Ligand protonation state significantly affects aggregation.
- Charged monomers show reduced electrostatic stabilization, disfavoring dimerization.
- Protonation redistributes electron density, lowering interfragment overlap and promoting dimer formation.
Conclusions:
- Ligand-controlled electronic structure is critical for aggregation behavior.
- Electrostatic and electronic factors interplay to govern copper hydride complex aggregation.
- Understanding aggregation is key to controlling reactivity in these complexes.
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