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Cyanate Formation via Photolytic Splitting of Dinitrogen
[Image: see text] Light-driven N(2) cleavage into molecular nitrides is an attractive strategy for synthetic nitrogen fixation. However, suitable platforms are rare. Furthermore, the development of catalytic protocols via this elementary step suffers from poor understanding of N–N photosplitting wit...
Autores principales: | , , , , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American
Chemical Society
2021
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8243327/ https://www.ncbi.nlm.nih.gov/pubmed/34240082 http://dx.doi.org/10.1021/jacsau.1c00117 |
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author | Schluschaß, Bastian Borter, Jan-Hendrik Rupp, Severine Demeshko, Serhiy Herwig, Christian Limberg, Christian Maciulis, Nicholas A. Schneider, Jessica Würtele, Christian Krewald, Vera Schwarzer, Dirk Schneider, Sven |
author_facet | Schluschaß, Bastian Borter, Jan-Hendrik Rupp, Severine Demeshko, Serhiy Herwig, Christian Limberg, Christian Maciulis, Nicholas A. Schneider, Jessica Würtele, Christian Krewald, Vera Schwarzer, Dirk Schneider, Sven |
author_sort | Schluschaß, Bastian |
collection | PubMed |
description | [Image: see text] Light-driven N(2) cleavage into molecular nitrides is an attractive strategy for synthetic nitrogen fixation. However, suitable platforms are rare. Furthermore, the development of catalytic protocols via this elementary step suffers from poor understanding of N–N photosplitting within dinitrogen complexes, as well as of the thermochemical and kinetic framework for coupled follow-up chemistry. We here present a tungsten pincer platform, which undergoes fully reversible, thermal N(2) splitting and reverse nitride coupling, allowing for experimental derivation of thermodynamic and kinetic parameters of the N–N cleavage step. Selective N–N splitting was also obtained photolytically. DFT computations allocate the productive excitations within the {WNNW} core. Transient absorption spectroscopy shows ultrafast repopulation of the electronic ground state. Comparison with ground-state kinetics and resonance Raman data support a pathway for N–N photosplitting via a nonstatistically vibrationally excited ground state that benefits from vibronically coupled structural distortion of the core. Nitride carbonylation and release are demonstrated within a full synthetic cycle for trimethylsilylcyanate formation directly from N(2) and CO. |
format | Online Article Text |
id | pubmed-8243327 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | American
Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-82433272021-07-06 Cyanate Formation via Photolytic Splitting of Dinitrogen Schluschaß, Bastian Borter, Jan-Hendrik Rupp, Severine Demeshko, Serhiy Herwig, Christian Limberg, Christian Maciulis, Nicholas A. Schneider, Jessica Würtele, Christian Krewald, Vera Schwarzer, Dirk Schneider, Sven JACS Au [Image: see text] Light-driven N(2) cleavage into molecular nitrides is an attractive strategy for synthetic nitrogen fixation. However, suitable platforms are rare. Furthermore, the development of catalytic protocols via this elementary step suffers from poor understanding of N–N photosplitting within dinitrogen complexes, as well as of the thermochemical and kinetic framework for coupled follow-up chemistry. We here present a tungsten pincer platform, which undergoes fully reversible, thermal N(2) splitting and reverse nitride coupling, allowing for experimental derivation of thermodynamic and kinetic parameters of the N–N cleavage step. Selective N–N splitting was also obtained photolytically. DFT computations allocate the productive excitations within the {WNNW} core. Transient absorption spectroscopy shows ultrafast repopulation of the electronic ground state. Comparison with ground-state kinetics and resonance Raman data support a pathway for N–N photosplitting via a nonstatistically vibrationally excited ground state that benefits from vibronically coupled structural distortion of the core. Nitride carbonylation and release are demonstrated within a full synthetic cycle for trimethylsilylcyanate formation directly from N(2) and CO. American Chemical Society 2021-05-20 /pmc/articles/PMC8243327/ /pubmed/34240082 http://dx.doi.org/10.1021/jacsau.1c00117 Text en © 2021 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Schluschaß, Bastian Borter, Jan-Hendrik Rupp, Severine Demeshko, Serhiy Herwig, Christian Limberg, Christian Maciulis, Nicholas A. Schneider, Jessica Würtele, Christian Krewald, Vera Schwarzer, Dirk Schneider, Sven Cyanate Formation via Photolytic Splitting of Dinitrogen |
title | Cyanate Formation via Photolytic Splitting of Dinitrogen |
title_full | Cyanate Formation via Photolytic Splitting of Dinitrogen |
title_fullStr | Cyanate Formation via Photolytic Splitting of Dinitrogen |
title_full_unstemmed | Cyanate Formation via Photolytic Splitting of Dinitrogen |
title_short | Cyanate Formation via Photolytic Splitting of Dinitrogen |
title_sort | cyanate formation via photolytic splitting of dinitrogen |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8243327/ https://www.ncbi.nlm.nih.gov/pubmed/34240082 http://dx.doi.org/10.1021/jacsau.1c00117 |
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