Gardner, Benedict M. and Balazs, Gabor and Scheer, Manfred and Wooles, Ashley J. and Tuna, Floriana and McInnes, Eric J. L. and McMaster, Jonathan and Lewis, William and Blake, Alexander J. and Liddle, Stephen T. (2015) Isolation of Elusive HAsAsH in a Crystalline Diuranium(IV) Complex. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 54 (50). pp. 15250-15254. ISSN 1433-7851, 1521-3773
Full text not available from this repository. (Request a copy)Abstract
The HAsAsH molecule has hitherto only been proposed tentatively as a short-lived species generated in electrochemical or microwave-plasma experiments. After two centuries of inconclusive or disproven claims of HAsAsH formation in the condensed phase, we report the isolation and structural authentication of HAsAsH in the diuranium(IV) complex [{U(Tren(TIPS))}(2)(mu-eta(2) :eta(2)-As2H2)] (3, Tren(TIPS) = N(CH2CH2NSiPr3i)(3); Pr-i = CH(CH3)(2)). Complex 3 was prepared by deprotonation and oxidative homocoupling of an arsenide precursor. Characterization and computational data are consistent with back-bonding-type interactions from uranium to the HAsAsH pi(*)-orbital. This experimentally confirms the theoretically predicted excellent p-acceptor character of HAsAsH, and is tantamount to full reduction to the diarsane-1,2- diide form.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | MAIN-GROUP ELEMENTS; ULTRAVIOLET-VISIBLE ELLIPSOMETRY; STRUCTURAL-CHARACTERIZATION; INFRARED-SPECTROSCOPY; CARBON-MONOXIDE; MULTIPLE BONDS; IN-SITU; URANIUM; CHEMISTRY; REACTIVITY; arsenic; back-bonding; density functional theory; diarsene; 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: | 29 Apr 2019 08:42 |
| Last Modified: | 29 Apr 2019 08:42 |
| URI: | https://pred.uni-regensburg.de/id/eprint/4295 |
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