Cyanate Formation via Photolytic Splitting of Dinitrogen
| Autor: | Jan-Hendrik Borter, Vera Krewald, Christian Würtele, Sven Schneider, Dirk Schwarzer, Christian Herwig, Jessica Schneider, Nicholas A. Maciulis, Bastian Schluschaß, Serhiy Demeshko, Severine Rupp, Christian Limberg |
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| Rok vydání: | 2021 |
| Předmět: |
Materials science
Photochemistry 010405 organic chemistry Kinetics Carbonylation Nitride 010402 general chemistry Resonance (chemistry) 01 natural sciences Article 0104 chemical sciences Chemistry symbols.namesake N2 Splitting Nitrogen Fixation Excited state Ultrafast laser spectroscopy symbols Ground state Spectroscopy Raman spectroscopy QD1-999 |
| Zdroj: | JACS Au Jacs Au JACS Au, Vol 1, Iss 6, Pp 879-894 (2021) |
| ISSN: | 2691-3704 |
| DOI: | 10.1021/jacsau.1c00117 |
| Popis: | Light-driven N2 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 N2 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 N2 and CO. |
| Databáze: | OpenAIRE |
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