Cyanate Formation via Photolytic Splitting of Dinitrogen.
Bastian SchluschaßJan-Hendrik BorterSeverine RuppSerhiy DemeshkoChristian HerwigChristian LimbergNicholas A MaciulisJessica SchneiderChristian WürteleVera KrewaldDirk SchwarzerSven SchneiderPublished in: JACS Au (2021)
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.
Keyphrases
- energy transfer
- quantum dots
- dna binding
- single molecule
- high throughput
- high resolution
- reduced graphene oxide
- room temperature
- big data
- crystal structure
- machine learning
- electron transfer
- blood brain barrier
- mass spectrometry
- aqueous solution
- deep learning
- molecular dynamics
- cerebral ischemia
- molecular docking
- clinical evaluation
- drug discovery