Uttendorfer, Maria K. and Hierlmeier, Gabriele and Balazs, Gabor and Wolf, Robert (2024) Access to 1,2,3-triphospholide ligands by reduction of di-tert-butyldiphosphatetrahedrane. DALTON TRANSACTIONS, 53 (24). pp. 10113-10119. ISSN 1477-9226, 1477-9234
Full text not available from this repository. (Request a copy)Abstract
Di-tert-butyldiphosphatetrahedrane (tBuCP)(2) (A) is a reactive tetrahedral molecule which may serve as a source of new phosphaorganic molecules and ligands. However, the redox chemistry of this compound has not yet been investigated. Here, we show that the reduction of A with alkali metals (AM = Li, Na, K, Rb and Cs) affords 1,2,3-triphospholides [AM(crown ether)][1,2,3-P(3)C(2)tBu(2)] (1-5, [AM(crown ether)] = [Li([12]crown-4)(2)](+), [Na([15]crown-5)(2)](+), [K([18]crown-6)](+), [Rb([18]crown-6)](+), and Cs+) with 1,3-diphospholides [AM(crown ether)][1,3-P(2)C(3)tBu(3)] (6-10) formed as by-products. The potassium salt 3 was isolated on a preparative scale, allowing for reactivity studies. Transmetalation with iron(II) and ruthenium(II) chlorides yielded the sandwich complexes [Cp*M(eta(5)-1,2,3-P(3)C(2)tBu(2))] (11, M = Fe; 12, M = Ru, Cp* = C5Me5) featuring eta(5)-coordinated triphospholide ligands. Treatment of 3 with [Cp2Fe][BAr4F] or [H(Et2O)(2)BAr4F] (BAr4F = B{C6H3(CF3)(2)}(4)) afforded the polyphosphorus compound tBu(4)C(4)P(6) (13), which presumably results from the dimerisation of a 1,2,3-triphospholyl radical intermediate (1,2,3-P(3)C(2)tBu(2))(center dot) (3(center dot)). Tetracyclic 13 is closely structurally related to an isomer of the hydrocarbon hypostrophene (C10H10).
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | TRIPHOSPHACYCLOBUTENIDE ION; P-4 ACTIVATION; PHOSPHORUS; CHEMISTRY; FERROCENE; EXISTENCE; ANIONS; |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie > Arbeitskreis Prof. Dr. Robert Wolf |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 17 Jul 2025 09:55 |
| Last Modified: | 17 Jul 2025 09:55 |
| URI: | https://pred.uni-regensburg.de/id/eprint/63550 |
Actions (login required)
 |
View Item |
