Isolation of elusive HAsAsH in a crystalline diuranium(IV) complex
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 authentica...
| Main Authors: | , , , , , , , , , |
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| Format: | Article |
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Wiley-VCH Verlag
2015
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| Online Access: | https://eprints.nottingham.ac.uk/46637/ |
| _version_ | 1848797373907599360 |
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| author | Gardner, Benedict M. Balázs, Gábor Scheer, Manfred Wooles, Ashley J. Tuna, Floriana McInnes, Eric J.L. McMaster, Jonathan Lewis, William Blake, Alexander J. Liddle, Stephen T. |
| author_facet | Gardner, Benedict M. Balázs, Gábor Scheer, Manfred Wooles, Ashley J. Tuna, Floriana McInnes, Eric J.L. McMaster, Jonathan Lewis, William Blake, Alexander J. Liddle, Stephen T. |
| author_sort | Gardner, Benedict M. |
| building | Nottingham Research Data Repository |
| collection | Online Access |
| description | 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(TrenTIPS)}2(μ-η2:η2-As2H2)] (3, TrenTIPS=N(CH2CH2NSiPri3)3; Pri=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 π*-orbital. This experimentally confirms the theoretically predicted excellent π-acceptor character of HAsAsH, and is tantamount to full reduction to the diarsane-1,2-diide form. |
| first_indexed | 2025-11-14T20:02:51Z |
| format | Article |
| id | nottingham-46637 |
| institution | University of Nottingham Malaysia Campus |
| institution_category | Local University |
| last_indexed | 2025-11-14T20:02:51Z |
| publishDate | 2015 |
| publisher | Wiley-VCH Verlag |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | nottingham-466372020-05-04T17:27:52Z https://eprints.nottingham.ac.uk/46637/ Isolation of elusive HAsAsH in a crystalline diuranium(IV) complex Gardner, Benedict M. Balázs, Gábor Scheer, Manfred Wooles, Ashley J. Tuna, Floriana McInnes, Eric J.L. McMaster, Jonathan Lewis, William Blake, Alexander J. Liddle, Stephen T. 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(TrenTIPS)}2(μ-η2:η2-As2H2)] (3, TrenTIPS=N(CH2CH2NSiPri3)3; Pri=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 π*-orbital. This experimentally confirms the theoretically predicted excellent π-acceptor character of HAsAsH, and is tantamount to full reduction to the diarsane-1,2-diide form. Wiley-VCH Verlag 2015-12-07 Article PeerReviewed Gardner, Benedict M., Balázs, Gábor, Scheer, Manfred, Wooles, Ashley J., Tuna, Floriana, McInnes, Eric J.L., McMaster, Jonathan, Lewis, William, 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 arsenic; back-bonding; density functional theory; diarsene; uranium https://doi.org/10.1002/anie.201508600 10.1002/anie.201508600 10.1002/anie.201508600 10.1002/anie.201508600 |
| spellingShingle | arsenic; back-bonding; density functional theory; diarsene; uranium Gardner, Benedict M. Balázs, Gábor Scheer, Manfred Wooles, Ashley J. Tuna, Floriana McInnes, Eric J.L. McMaster, Jonathan Lewis, William Blake, Alexander J. Liddle, Stephen T. Isolation of elusive HAsAsH in a crystalline diuranium(IV) complex |
| title | Isolation of elusive HAsAsH in a crystalline diuranium(IV) complex |
| title_full | Isolation of elusive HAsAsH in a crystalline diuranium(IV) complex |
| title_fullStr | Isolation of elusive HAsAsH in a crystalline diuranium(IV) complex |
| title_full_unstemmed | Isolation of elusive HAsAsH in a crystalline diuranium(IV) complex |
| title_short | Isolation of elusive HAsAsH in a crystalline diuranium(IV) complex |
| title_sort | isolation of elusive hasash in a crystalline diuranium(iv) complex |
| topic | arsenic; back-bonding; density functional theory; diarsene; uranium |
| url | https://eprints.nottingham.ac.uk/46637/ https://eprints.nottingham.ac.uk/46637/ https://eprints.nottingham.ac.uk/46637/ |