Supramolecular architecture of [AsPh2Br2]2[(Br3)−…(Br2)…(Br3)−] obtained by bromination of (AsPh2)2S

Bromination of (AsPh2)2S leads to cleavage of the sulfide bridge to give AsPh2Br when 1 mol of bromine is used but with 2 mols the product is the polybromide, [AsPh2Br2]2[Br8], containing the previously unknown [AsPh2Br2]+ cation and a rare [(Br3)−…(Br2)…(Br3)−] ensemble whose short (yet not covalen...

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Main Authors: Silaghi-Dumitrescu, Luminita, Attia, Amr A.A., Silaghi-Dumitrescu, Radu, Blake, Alexander J., Sowerby, D. Bryan
Format: Article
Published: Elsevier 2017
Subjects:
Online Access:https://eprints.nottingham.ac.uk/47813/
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author Silaghi-Dumitrescu, Luminita
Attia, Amr A.A.
Silaghi-Dumitrescu, Radu
Blake, Alexander J.
Sowerby, D. Bryan
author_facet Silaghi-Dumitrescu, Luminita
Attia, Amr A.A.
Silaghi-Dumitrescu, Radu
Blake, Alexander J.
Sowerby, D. Bryan
author_sort Silaghi-Dumitrescu, Luminita
building Nottingham Research Data Repository
collection Online Access
description Bromination of (AsPh2)2S leads to cleavage of the sulfide bridge to give AsPh2Br when 1 mol of bromine is used but with 2 mols the product is the polybromide, [AsPh2Br2]2[Br8], containing the previously unknown [AsPh2Br2]+ cation and a rare [(Br3)−…(Br2)…(Br3)−] ensemble whose short (yet not covalent) Br2…Br3 contacts have previously supported tentative description as an octabromide Br82− anion. X-ray crystallography shows that the compound has a three dimensional supramolecular structure based on cooperativity of weak intermolecular Csingle bondH…π, Csingle bondH…Br hydrogen bonds and secondary Br…Br interactions in the solid state. The electronic structure and the stability of the [AsPh2Br2]2[Br8] are rationalized using DFT and HF calculations and molecular orbital considerations.
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publishDate 2017
publisher Elsevier
recordtype eprints
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spelling nottingham-478132020-05-04T19:04:11Z https://eprints.nottingham.ac.uk/47813/ Supramolecular architecture of [AsPh2Br2]2[(Br3)−…(Br2)…(Br3)−] obtained by bromination of (AsPh2)2S Silaghi-Dumitrescu, Luminita Attia, Amr A.A. Silaghi-Dumitrescu, Radu Blake, Alexander J. Sowerby, D. Bryan Bromination of (AsPh2)2S leads to cleavage of the sulfide bridge to give AsPh2Br when 1 mol of bromine is used but with 2 mols the product is the polybromide, [AsPh2Br2]2[Br8], containing the previously unknown [AsPh2Br2]+ cation and a rare [(Br3)−…(Br2)…(Br3)−] ensemble whose short (yet not covalent) Br2…Br3 contacts have previously supported tentative description as an octabromide Br82− anion. X-ray crystallography shows that the compound has a three dimensional supramolecular structure based on cooperativity of weak intermolecular Csingle bondH…π, Csingle bondH…Br hydrogen bonds and secondary Br…Br interactions in the solid state. The electronic structure and the stability of the [AsPh2Br2]2[Br8] are rationalized using DFT and HF calculations and molecular orbital considerations. Elsevier 2017-08-31 Article PeerReviewed Silaghi-Dumitrescu, Luminita, Attia, Amr A.A., Silaghi-Dumitrescu, Radu, Blake, Alexander J. and Sowerby, D. Bryan (2017) Supramolecular architecture of [AsPh2Br2]2[(Br3)−…(Br2)…(Br3)−] obtained by bromination of (AsPh2)2S. Inorganica Chimica Acta . ISSN 0020-1693 (In Press) arsenic bromine Br8 arsonium crystal structure DFT supramolecular http://www.sciencedirect.com/science/article/pii/S0020169317311210 doi:10.1016/j.ica.2017.08.052 doi:10.1016/j.ica.2017.08.052
spellingShingle arsenic
bromine
Br8
arsonium
crystal structure
DFT
supramolecular
Silaghi-Dumitrescu, Luminita
Attia, Amr A.A.
Silaghi-Dumitrescu, Radu
Blake, Alexander J.
Sowerby, D. Bryan
Supramolecular architecture of [AsPh2Br2]2[(Br3)−…(Br2)…(Br3)−] obtained by bromination of (AsPh2)2S
title Supramolecular architecture of [AsPh2Br2]2[(Br3)−…(Br2)…(Br3)−] obtained by bromination of (AsPh2)2S
title_full Supramolecular architecture of [AsPh2Br2]2[(Br3)−…(Br2)…(Br3)−] obtained by bromination of (AsPh2)2S
title_fullStr Supramolecular architecture of [AsPh2Br2]2[(Br3)−…(Br2)…(Br3)−] obtained by bromination of (AsPh2)2S
title_full_unstemmed Supramolecular architecture of [AsPh2Br2]2[(Br3)−…(Br2)…(Br3)−] obtained by bromination of (AsPh2)2S
title_short Supramolecular architecture of [AsPh2Br2]2[(Br3)−…(Br2)…(Br3)−] obtained by bromination of (AsPh2)2S
title_sort supramolecular architecture of [asph2br2]2[(br3)−…(br2)…(br3)−] obtained by bromination of (asph2)2s
topic arsenic
bromine
Br8
arsonium
crystal structure
DFT
supramolecular
url https://eprints.nottingham.ac.uk/47813/
https://eprints.nottingham.ac.uk/47813/
https://eprints.nottingham.ac.uk/47813/