Magnall, Rosie and Balazs, Gabor and Lu, Erli and Tuna, Florian and Wooles, Ashley J. and Scheer, Manfred and Liddle, Stephen T. (2019) Trapping of a Highly Bent and Reduced Form of 2-Phosphaethynolate in a Mixed-Valence Diuranium-Triamidoamine Complex. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 58 (30). pp. 10215-10219. ISSN 1433-7851, 1521-3773
Full text not available from this repository. (Request a copy)Abstract
The chemistry of 2-phosphaethynolate is burgeoning, but there remains much to learn about this ligand, for example its reduction chemistry is scarce as this promotes P-C-O fragmentations or couplings. Here, we report that reduction of [U(Tren(TIPS))(OCP)] (Tren(TIPS)=N(CH2CH2NSiPr3i)(3)) with KC8/2,2,2-cryptand gives [{U(Tren(TIPS))}(2){mu-eta(2)(OP):eta(2)(CP)-OCP}][K(2,2,2-cryptand)]. The coordination mode of this trapped 2-phosphaethynolate is unique, and derives from an unprecedented highly reduced and highly bent form of this ligand with the most acute P-C-O angle in any complex to date (P-C-O measured angle approximate to 127 degrees). The characterisation data support a mixed-valence diuranium(III/IV) formulation, where backbonding from uranium gives a highly reduced form of the P-C-O unit that is perhaps best described as a uranium-stabilised OCP2-. radical dianion. Quantum chemical calculations reveal that this gives unprecedented carbene character to the P-C-O unit, which engages in a weak donor-acceptor interaction with one of the uranium ions.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | OXALATE FORMATION; URANIUM; PHOSPHAETHYNOLATE; ACTIVATION; PHOSPHIDE; EARTH; AN=U; PCO; CP; 2-phosphaethynolate; carbene; DFT calculations; mixed-valence complexes; uranium |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie > Chair Prof. Dr. Manfred Scheer |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 07 Apr 2020 08:14 |
| Last Modified: | 07 Apr 2020 08:14 |
| URI: | https://pred.uni-regensburg.de/id/eprint/26615 |
Actions (login required)
 |
View Item |
