English
 
Help Privacy Policy Disclaimer
  Advanced SearchBrowse

Item

ITEM ACTIONSEXPORT
  Cyanate formation via photolytic splitting of dinitrogen

Schluschaß, B., Borter, J.-H., Rupp, S., Demeshko, S., Herwig, C., Limberg, C., et al. (2021). Cyanate formation via photolytic splitting of dinitrogen. JACS Au, 1(6), 879-894. doi:10.1021/jacsau.1c00117.

Item is

Basic

show hide
Genre: Journal Article

Files

show Files
hide Files
:
3383564.pdf (Publisher version), 5MB
Name:
3383564.pdf
Description:
-
Visibility:
Public
MIME-Type / Checksum:
application/pdf / [MD5]
Technical Metadata:
Copyright Date:
-
Copyright Info:
-

Locators

show

Creators

show
hide
 Creators:
Schluschaß, B., Author
Borter, J.-H.1, Author              
Rupp, S., Author
Demeshko, S., Author
Herwig, C., Author
Limberg, C., Author
Maciulis, N. A., Author
Schneider, J., Author
Würtele, C., Author
Krewald, V., Author
Schwarzer, D.1, Author              
Schneider, S., Author
Affiliations:
1Department of Dynamics at Surfaces, MPI for Biophysical Chemistry, Max Planck Society, ou_578600              

Content

show
hide
Free keywords: Nitrogen Fixation, Nitride, N2 Splitting, Photochemistry, Carbonylation
 Abstract: 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.

Details

show
hide
Language(s): eng - English
 Dates: 2021-03-132021-05-202021-06-28
 Publication Status: Published in print
 Pages: -
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/jacsau.1c00117
 Degree: -

Event

show

Legal Case

show

Project information

show

Source 1

show
hide
Title: JACS Au
Source Genre: Journal
 Creator(s):
Affiliations:
Publ. Info: -
Pages: - Volume / Issue: 1 (6) Sequence Number: - Start / End Page: 879 - 894 Identifier: ISSN: 2691-3704