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Rational Design of a Phosphorus-Centered Disbiradical.
- Source :
-
Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2024 Mar 04; Vol. 63 (10), pp. e202318210. Date of Electronic Publication: 2024 Jan 19. - 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) <subscript>2</subscript> P-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) <subscript>2</subscript> P⋅] (1) was treated with 1,6-dibromohexane, affording the brominated species {Br[P(μ-NTer)] <subscript>2</subscript> } <subscript>2</subscript> C <subscript>6</subscript> H <subscript>12</subscript> (3). Subsequent reduction with KC <subscript>8</subscript> led to the formation of the disbiradical {⋅[P(μ-NTer)] <subscript>2</subscript> } <subscript>2</subscript> C <subscript>6</subscript> H <subscript>12</subscript> (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 <superscript>-</superscript> ). Moreover, 4 could be used in small molecule activation.<br /> (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)
Details
- Language :
- English
- ISSN :
- 1521-3773
- Volume :
- 63
- Issue :
- 10
- Database :
- MEDLINE
- Journal :
- Angewandte Chemie (International ed. in English)
- Publication Type :
- Academic Journal
- Accession number :
- 38117661
- Full Text :
- https://doi.org/10.1002/anie.202318210