Rookes, Thomas M. and Gardner, Benedict M. and Balazs, Gabor and Gregson, Matthew and Tuna, Floriana and Wooles, Ashley J. and Scheer, Manfred and Liddle, Stephen T. (2017) Crystalline Diuranium Phosphinidiide and mu-Phosphido Complexes with Symmetric and Asymmetric UPU Cores. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 56 (35). pp. 10495-10500. ISSN 1433-7851, 1521-3773
Full text not available from this repository. (Request a copy)Abstract
Reaction of [U(Tren(TIPS))(PH2)] (1, Tren(TIPS)=N(CH(2)CH(2)NSiPri(3))(3)) with C6H5CH2K and [U(Tren(TIPS))(THF)][BPh4] (2) afforded a rare diuranium parent phosphinidiide complex [{U(Tren(TIP)S)}(2)(mu-PH)] (3). Treatment of 3 with C6H5CH2K and two equivalents of benzo-15-crown-5 ether (B15C5) gave the diuranium mu-phosphido complex [{U(Tren(TIPS))}2(mu-P)][K(B15C5)(2)] (4). Alternatively, reaction of [U(Tren(TIPS))(PH)][Na(12C(4))(2)] (5, 12C(4)=12-crown-4 ether) with [U{N(CH2CH2NSiMe2But)(2)CH2CH2NSi(Me)(CH2)(Bu-t)}] (6) produced the diuranium mu-phosphido complex [{U(Tren(TIPS))}(mu-P){U(Tren(DMBS))}][Na(12C(4))(2)] [7, Tren(DMBS)=N(CH2CH2NSiMe2But)(3)]. Compounds 4 and 7 are unprecedented examples of uranium phosphido complexes outside of matrix isolation studies, and they rapidly decompose in solution underscoring the paucity of uranium phosphido complexes. Interestingly, 4 and 7 feature symmetric and asymmetric UPU cores, respectively, reflecting their differing steric profiles.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | PHOSPHORUS TRIPLE BOND; URANIUM COMPLEXES; TRIAMIDOAMINE COMPLEXES; TERMINAL PHOSPHIDE; METALLA-ALLENES; TRANS-INFLUENCE; MULTIPLE BONDS; OXO COMPLEX; URANYL-ION; U-IV=C; density functional theory; metal-ligand multiple bonding; phosphido; phosphinidiide; 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: | 14 Dec 2018 13:16 |
| Last Modified: | 11 Feb 2019 14:33 |
| URI: | https://pred.uni-regensburg.de/id/eprint/1373 |
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