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Facile Synthesis of a Stable Side-on Phosphinyne Complex by Redox Driven Intramolecular Cyclisation
- Source :
- Chemistry (Weinheim an Der Bergstrasse, Germany)
- Publication Year :
- 2019
-
Abstract
- Alkyne complexes with vicinal substitution by a Lewis acid and a Lewis base at the coordinated alkyne are prospective frustrated Lewis pairs exhibiting a particular mutual distance and, hence, a specific activation potential. In this contribution, investigations on the generation of a WII alkyne complex bearing a phosphine as Lewis base and a carbenium group as Lewis acid are presented. Independently on potential substrates added, an intramolecular cyclisation product was always isolated. A subsequent deprotonation step led to an unprecedented side‐on λ5‐phosphinyne complex, which is interpreted as highly zwitterionic according to visible absorption spectroscopy supported by TD‐DFT. Low‐temperature 31P NMR and EPR spectroscopic measurements combined with time‐dependent IR‐spectroscopic monitoring provided insights in the mechanism of the cyclisation reaction. Decomposition of the multicomponent IR spectra by multivariate curve resolution and a kinetic hard‐modelling approach allowed the derivation of kinetic parameters. Assignment of the individual IR spectra to potential intermediates was provided by DFT calculations.<br />A sought‐after combination of a phosphine as Lewis base and a carbenium centre as Lewis acid at a WII alkyne complex turned out to be stable as a diradical. Intramolecular cyclisation and subsequent deprotonation provided a side‐on complex of a λ5‐1‐phospha‐2,3‐didehydrofluoranthene, which can be denoted as λ5‐phosphinyne.
- Subjects :
- chemistry.chemical_classification
Full Paper
Chemistry
phosphinyne complex
Organic Chemistry
frustrated Lewis pair
Infrared spectroscopy
Alkyne
General Chemistry
non-innocent ligand
Full Papers
Catalysis
Frustrated Lewis pair
Non-innocent ligand
cyclisation mechanism
chemistry.chemical_compound
Deprotonation
Computational chemistry
Intramolecular force
Lewis acids and bases
Frustrated Lewis Pairs
Phosphine
alkyne complex
Subjects
Details
- ISSN :
- 15213765
- Volume :
- 26
- Issue :
- 50
- Database :
- OpenAIRE
- Journal :
- Chemistry (Weinheim an der Bergstrasse, Germany)
- Accession number :
- edsair.doi.dedup.....e2ad8143739463131805bcfcb4db2976