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Rational Design of a Phosphorus‐Centered Disbiradical.
- Source :
-
Angewandte Chemie International Edition . 3/4/2024, Vol. 63 Issue 10, p1-7. 7p. - Publication Year :
- 2024
-
Abstract
- Phosphorus‐centered disbiradicals, in which the radical sites exist as individual spin doublets with weak spin‐spin interaction have not been known so far. Starting from monoradicals of the type [⋅P(μ‐NTer)2P−R], we have now succeeded in linking two such monoradical phosphorus centers by appropriate choice of a linker. To this end, biradical [⋅P(μ‐NTer)2P⋅] (1) was treated with 1,6‐dibromohexane, affording the brominated species {Br[P(μ‐NTer)]2}2C6H12 (3). Subsequent reduction with KC8 led to the formation of the disbiradical {⋅[P(μ‐NTer)]2}2C6H12 (4) featuring a large distance between the radical phosphorus sites in the solid state and formally the highest biradical character observed in a P‐centered biradical so far, approaching 100 %. EPR spectroscopy revealed a three‐line signal in solution with a considerably larger exchange interaction than would be expected from the molecular structure of the single crystal. Quantum chemical calculations revealed a highly dynamic conformational space; thus, the two radical sites can approach each other with a much smaller distance in solution. Further reduction of 4 resulted in the formation of a potassium salt featuring the first structurally characterized P‐centered distonic radical anion (5−). Moreover, 4 could be used in small molecule activation. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 14337851
- Volume :
- 63
- Issue :
- 10
- Database :
- Academic Search Index
- Journal :
- Angewandte Chemie International Edition
- Publication Type :
- Academic Journal
- Accession number :
- 175671290
- Full Text :
- https://doi.org/10.1002/anie.202318210