Synthesis and Thermally and Light Driven Cleavage of an N‐Heterocyclic Diphosphine with Inorganic Backbone
| Autor: | Christoph M. Feil, Dietrich Gudat, Markus Blum, Martin Nieger |
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| Přispěvatelé: | Department of Chemistry |
| Rok vydání: | 2020 |
| Předmět: |
MECHANISM
Phosphines Radical 116 Chemical sciences 010402 general chemistry Cleavage (embryo) 01 natural sciences Inorganic Chemistry Polymer chemistry ELEMENTS Bond energy Photolysis 010405 organic chemistry Chemistry Photodissociation GAUSSIAN-BASIS SETS Radicals DISSOCIATION RESONANCE REACTIVITY 0104 chemical sciences CORRELATED MOLECULAR CALCULATIONS PHOSPHORUS Light driven PERSISTENT PHOSPHINYL RADICALS Dimerization |
| Zdroj: | Zeitschrift für anorganische und allgemeine Chemie. 647:279-285 |
| ISSN: | 1521-3749 0044-2313 |
| DOI: | 10.1002/zaac.202000252 |
| Popis: | A diphosphine with an unsupported PP bond connecting two carbon-free "inorganic" 1,3,2,4,5-diazaphosphadisilolidine rings was prepared by reductive coupling of a P-chloro-substituted monocyclic precursor molecule. VT-EPR studies revealed that the diphosphine exists in solution, like other compounds of this kind, in dynamic equilibrium with the corresponding phosphinyl radicals. Determination of the radical concentration from the EPR spectra permitted to calculate thermochemical parameters for the homolytic PP bond fission. The results disclose that both the enthalpy and entropy of dissociation are higher than in topologically related bi(diazaphospholidines). The impact of the entropy term allows explaining that, regardless of the presence of an energetically rather stable PP bond, the onset of dissociation is observable even at ambient temperature. Irradiation experiments showed that radical formation cannot only be induced thermally, but also by photolysis. |
| Databáze: | OpenAIRE |
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