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Crystal structures of 2-bromo-1,1,1,3,3,3-hexamethyl-2-(trimethylsilyl)trisilane and 2-bromo-1,1,1,3,3,3-hexaisopropyl-2-(triisopropylsilyl)trisilane
The synthesis and crystal structures of two tris(trialkylsilyl)silyl bromide compounds, C(9)H(27)BrSi(4) (I, HypSiBr) and C(27)H(63)BrSi(4) (II, TipSiBr), are described. Compound I was prepared in 85% yield by free-radical bromination of 1,1,1,3,3,3-hexamethyl-2-(trimethylsilyl)trisilane us...
Autores principales: | , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
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International Union of Crystallography
2018
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6072994/ https://www.ncbi.nlm.nih.gov/pubmed/30116580 http://dx.doi.org/10.1107/S2056989018009696 |
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author | Gulotty, Eva M. Staples, Richard J. Biros, Shannon M. Gaspar, Peter P. Rath, Nigam P. Winchester, William R. |
author_facet | Gulotty, Eva M. Staples, Richard J. Biros, Shannon M. Gaspar, Peter P. Rath, Nigam P. Winchester, William R. |
author_sort | Gulotty, Eva M. |
collection | PubMed |
description | The synthesis and crystal structures of two tris(trialkylsilyl)silyl bromide compounds, C(9)H(27)BrSi(4) (I, HypSiBr) and C(27)H(63)BrSi(4) (II, TipSiBr), are described. Compound I was prepared in 85% yield by free-radical bromination of 1,1,1,3,3,3-hexamethyl-2-(trimethylsilyl)trisilane using bromobutane and 2,2′-azobis(2-methylpropionitrile) as a radical initiator at 333 K. The molecule possesses threefold rotational symmetry, with the central Si atom and the Br atom being located on the threefold rotation axis. The Si—Br bond distance is 2.2990 (12) Å and the Si—Si bond lengths are 2.3477 (8) Å. The Br—Si—Si bond angles are 104.83 (3)° and the Si—Si—Si bond angles are 113.69 (2)°, reflecting the steric hindrance inherent in the three trimethylsilyl groups attached to the central Si atom. Compound II was prepared in 55% yield by free-radical bromination of 1,1,1,3,3,3-hexaisopropyl-2-(triisopropylsilyl)trisilane using N-bromosuccinimide and 2,2′-azobis(2-methylpropionitrile) as a radical initiator at 353 K. Here the Si—Br bond length is 2.3185 (7) Å and the Si—Si bond lengths range from 2.443 (1) to 2.4628 (9) Å. The Br—Si—Si bond angles range from 98.44 (3) to 103.77 (3)°, indicating steric hindrance between the three triisopropylsilyl groups. |
format | Online Article Text |
id | pubmed-6072994 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2018 |
publisher | International Union of Crystallography |
record_format | MEDLINE/PubMed |
spelling | pubmed-60729942018-08-16 Crystal structures of 2-bromo-1,1,1,3,3,3-hexamethyl-2-(trimethylsilyl)trisilane and 2-bromo-1,1,1,3,3,3-hexaisopropyl-2-(triisopropylsilyl)trisilane Gulotty, Eva M. Staples, Richard J. Biros, Shannon M. Gaspar, Peter P. Rath, Nigam P. Winchester, William R. Acta Crystallogr E Crystallogr Commun Research Communications The synthesis and crystal structures of two tris(trialkylsilyl)silyl bromide compounds, C(9)H(27)BrSi(4) (I, HypSiBr) and C(27)H(63)BrSi(4) (II, TipSiBr), are described. Compound I was prepared in 85% yield by free-radical bromination of 1,1,1,3,3,3-hexamethyl-2-(trimethylsilyl)trisilane using bromobutane and 2,2′-azobis(2-methylpropionitrile) as a radical initiator at 333 K. The molecule possesses threefold rotational symmetry, with the central Si atom and the Br atom being located on the threefold rotation axis. The Si—Br bond distance is 2.2990 (12) Å and the Si—Si bond lengths are 2.3477 (8) Å. The Br—Si—Si bond angles are 104.83 (3)° and the Si—Si—Si bond angles are 113.69 (2)°, reflecting the steric hindrance inherent in the three trimethylsilyl groups attached to the central Si atom. Compound II was prepared in 55% yield by free-radical bromination of 1,1,1,3,3,3-hexaisopropyl-2-(triisopropylsilyl)trisilane using N-bromosuccinimide and 2,2′-azobis(2-methylpropionitrile) as a radical initiator at 353 K. Here the Si—Br bond length is 2.3185 (7) Å and the Si—Si bond lengths range from 2.443 (1) to 2.4628 (9) Å. The Br—Si—Si bond angles range from 98.44 (3) to 103.77 (3)°, indicating steric hindrance between the three triisopropylsilyl groups. International Union of Crystallography 2018-07-24 /pmc/articles/PMC6072994/ /pubmed/30116580 http://dx.doi.org/10.1107/S2056989018009696 Text en © Gulotty et al. 2018 http://creativecommons.org/licenses/by/2.0/uk/ This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.http://creativecommons.org/licenses/by/2.0/uk/ |
spellingShingle | Research Communications Gulotty, Eva M. Staples, Richard J. Biros, Shannon M. Gaspar, Peter P. Rath, Nigam P. Winchester, William R. Crystal structures of 2-bromo-1,1,1,3,3,3-hexamethyl-2-(trimethylsilyl)trisilane and 2-bromo-1,1,1,3,3,3-hexaisopropyl-2-(triisopropylsilyl)trisilane |
title | Crystal structures of 2-bromo-1,1,1,3,3,3-hexamethyl-2-(trimethylsilyl)trisilane and 2-bromo-1,1,1,3,3,3-hexaisopropyl-2-(triisopropylsilyl)trisilane |
title_full | Crystal structures of 2-bromo-1,1,1,3,3,3-hexamethyl-2-(trimethylsilyl)trisilane and 2-bromo-1,1,1,3,3,3-hexaisopropyl-2-(triisopropylsilyl)trisilane |
title_fullStr | Crystal structures of 2-bromo-1,1,1,3,3,3-hexamethyl-2-(trimethylsilyl)trisilane and 2-bromo-1,1,1,3,3,3-hexaisopropyl-2-(triisopropylsilyl)trisilane |
title_full_unstemmed | Crystal structures of 2-bromo-1,1,1,3,3,3-hexamethyl-2-(trimethylsilyl)trisilane and 2-bromo-1,1,1,3,3,3-hexaisopropyl-2-(triisopropylsilyl)trisilane |
title_short | Crystal structures of 2-bromo-1,1,1,3,3,3-hexamethyl-2-(trimethylsilyl)trisilane and 2-bromo-1,1,1,3,3,3-hexaisopropyl-2-(triisopropylsilyl)trisilane |
title_sort | crystal structures of 2-bromo-1,1,1,3,3,3-hexamethyl-2-(trimethylsilyl)trisilane and 2-bromo-1,1,1,3,3,3-hexaisopropyl-2-(triisopropylsilyl)trisilane |
topic | Research Communications |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6072994/ https://www.ncbi.nlm.nih.gov/pubmed/30116580 http://dx.doi.org/10.1107/S2056989018009696 |
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