Development of Phosphorus Compounds and Organometallic Complexes: A Hybrid Computational and Experimental Approach
Embargoed until 2025-11-20
Author
Date
2024Type
- Doctoral Thesis
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yes
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Abstract
The following thesis highlights the importance of combining experimental techniques with computational studies, an essential approach in chemical research. This general strategy is particularly useful for understanding molecular structures, bond energies, and reaction barriers. The work presented here emphasizes the importance of selecting appropriate methods to effectively use theoretical and computational resources to understand chemical processes. This thesis presents several examples of this approach, using a hybrid methodology that combines experimental and density functional theory (DFT) strategies to study organometallic complexes and organophosphorus compounds.
Chapters 2 and 3 provide computational analysis of catalytic reactions in three distinct areas. The first involves the use of hydrogen to reduce nitrogen oxides with Rh(I), Ir(I), and Rh(I)–Pt(II) complexes. The second area explores the dehydropolymerization of ammonia–borane using Rh(I)–Rh(I) complexes. The third study focuses on the catalytic hydrophosphination of olefins using a Mn(I) complex. These DFT studies, combined with spectroscopic and structural analyses, have helped to elucidate the catalytic mechanisms of organometallic complexes in mitigating nitrogen oxides, selectively dehydrogenating ammonia–borane for efficient access to chemically stored hydrogen, and selectively producing BN-enriched compounds, as well as synthesizing challenging phosphorus-containing chemicals.
Chapter 4 presents the synthesis and analysis of trityl–phosphorus compounds and the development of various acylphosphane oxides as potential photoinitiators. Various spectroscopic techniques and TD-DFT analysis were used to understand the photochemistry of these compounds and their performance as photoinitiators.
Chapter 5 applies computational techniques to understand the mechanisms and reaction modes of PC- and PCN-containing compounds. The first study in this chapter uses DFT to explore the reactivity of compounds containing a 1-phospha-3-aza-allene unit and their spectroscopic characteristics. The second study focuses on the reactivity of 2-phosphanaphthalene derivatives and their copper complexes for synthesizing (–P–C–)n polymeric compounds. The combined theoretical and experimental approach has helped to elucidate unusual reaction modes and remarkable reactivity of these compounds.
In conclusion, this thesis demonstrates that the hybrid computational-experimental approach, with DFT at its core, is invaluable in enhancing our understanding of the chemical transformations of organophosphorus compounds and the reaction mechanisms involving organometallic complexes. This approach continues to be a constructive collaboration of theory and experiment. Show more
Permanent link
https://doi.org/10.3929/ethz-b-000706266Publication status
publishedExternal links
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Publisher
ETH ZurichSubject
Organometallic catalysis; Photoinitiators; Organophosphorus compoundsOrganisational unit
03447 - Grützmacher, Hansjörg (emeritus) / Grützmacher, Hansjörg (emeritus)
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ETH Bibliography
yes
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