Hierlmeier, Gabriele and Kutta, Roger Jan and Coburger, Peter and Stammler, Hans-Georg and Schwabedissen, Jan and Mitzel, Norbert W. and Dimitrova, Maria and Berger, Raphael J. F. and Nuernberger, Patrick and Wolf, Robert (2024) Structure and photochemistry of di-tert-butyldiphosphatetrahedrane. CHEMICAL SCIENCE, 15 (15). pp. 5596-5603. ISSN 2041-6520, 2041-6539
Full text not available from this repository. (Request a copy)Abstract
Di-tert-butyldiphosphatetrahedrane (tBuCP)(2) (1) is a mixed carbon- and phosphorus-based tetrahedral molecule, isolobal to white phosphorus (P-4). However, despite the fundamental significance and well-explored reactivity of the latter molecule, the precise structure of the free (tBuCP)(2) molecule (1) and a detailed analysis of its electronic properties have remained elusive. Here, single-crystal X-ray structure determination of 1 at low temperature confirms the tetrahedral structure. Furthermore, quantum chemical calculations confirm that 1 is isolobal to P-4 and shows a strong largely isotropic diamagnetic response in the magnetic field and thus pronounced spherical aromaticity. A spectroscopic and computational study on the photochemical reactivity reveals that diphosphatetrahedrane 1 readily dimerises to the ladderane-type phosphaalkyne tetramer (tBuCP)(4) (2) under irradiation with UV light. With sufficient thermal activation energy, the dimerisation proceeds also in the dark. In both cases, an isomerisation to a 1,2-diphosphacyclobutadiene 1 ' is the first step. This intermediate subsequently undergoes a [2 + 2] cycloaddition with a second 1,2-diphosphacyclobutadiene molecule to form 2. The 1,2-diphosphacyclobutadiene intermediate 1 ' can be trapped chemically by N-methylmaleimide as an alternative [2 + 2] cycloaddition partner.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | COVALENT RADII; ELECTRONIC-STRUCTURES; MOLECULES; DIMERIZATION; AROMATICITY; SINGLE; DFT; |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie > Arbeitskreis Prof. Dr. Robert Wolf Chemistry and Pharmacy > Institut für Physikalische und Theoretische Chemie > Chair of Physical Chemistry I > Prof. Dr. Patrick Nürnberger |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 29 Jul 2025 05:36 |
| Last Modified: | 29 Jul 2025 05:36 |
| URI: | https://pred.uni-regensburg.de/id/eprint/63930 |
Actions (login required)
 |
View Item |
