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Coordination isomerism in dioxophosphorane cyanides
Ayu Afiqah Nasrullah1,2, Edgar Zander1, Fabian Dankert3
1Leibniz Institut für Katalyse e.V. (LIKAT) A.-Einstein-Str. 29a 18059 Rostock Germany christian.hering-junghans@catalysis.de eszter.barath@catalysis.de.
The study details alkali metal cyanophosphides and their reactions. Oxidation with oxygen reveals coordination isomerism in dioxophosphoranes, unlike sulfur oxidation.
Area of Science:
- Organometallic Chemistry
- Main Group Chemistry
- Phosphorus Chemistry
Background:
- 1,3-phosphaazaallenes are thermally labile, forming cyanophosphines.
- Deprotonation of cyanophosphines yields cyanophosphides.
- Alkali metal cyanophosphides exhibit structural diversity.
Purpose of the Study:
- Synthesize and characterize alkali metal tethered cyanophosphides.
- Investigate the reactivity of cyanophosphides with oxidants.
- Explore coordination isomerism in oxidation products.
Main Methods:
- Synthesis of alkali metal cyanophosphides with crown ethers.
- Oxidation reactions using O2, S8, and N2O.
- X-ray crystallography for structural determination.
- Computational studies (DFT) for theoretical insights.
Main Results:
- Isolation of alkali metal tethered cyanophosphides [(DippTerPCN)M(crown)].
- Formation of dioxophosphoranes [DippTerPO2(CN)]- via oxidation with O2, exhibiting cyanide/isocyanide isomerism.
- Synthesis of dithiophosphorane [DippTerPS2(CN)]- without isomerism.
- Generation of anionic phoshinidene monoxide adducts using N2O.
Conclusions:
- Alkali metal cyanophosphides are versatile synthons.
- Triplet oxygen plays a key role in inducing coordination isomerism.
- Cyanide isomer is thermodynamically favored over isocyanide.
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