Donor‐Stabilised [SbF4]+: SbF5 as a Fluoride‐Ion Donor
Antimony pentafluoride is a strong Lewis acid and fluoride‐ion acceptor that has not previously demonstrated any discreet fluoride‐ion donor properties. The first donor‐stabilised [SbF4]+ cations were prepared from the autoionisation of SbF5 in the presence of bidentate N‐donor ligands 2,2’‐bipyridi...
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creator | O'Donnell, Felix Turnbull, Douglas Wetmore, Stacey D. Gerken, Michael |
description | Antimony pentafluoride is a strong Lewis acid and fluoride‐ion acceptor that has not previously demonstrated any discreet fluoride‐ion donor properties. The first donor‐stabilised [SbF4]+ cations were prepared from the autoionisation of SbF5 in the presence of bidentate N‐donor ligands 2,2’‐bipyridine (bipy) and 1,10‐phenanthroline (phen) as their [SbF6]− salts. The [SbF4(N−N)][Sb2F11] (N−N=bipy, phen) salts were synthesised by the addition of one equivalent of SbF5⋅SO2 to [SbF4(N−N)][SbF6] in liquid SO2. The salts show remarkable stability and were characterised by Raman spectroscopy and multinuclear NMR spectroscopy. The crystal structures of [SbF4(phen)][SbF6] ⋅ 3CH3CN and [SbF4(phen)][SbF6] ⋅ 2SO2 were determined, showing distorted octahedral cations. DFT calculations and NBO analyses reveal that significant degree of electron‐pair donation from N to Sb stabilizes [SbF4]+ with the Sb−N bond strength being approximately two thirds of that of the Sb−F bonds in these cations and the cationic charge being primarily ligand‐centred.
The ability of the strong Lewis acid SbF5 to act as a fluoride‐ion donor has been demonstrated for the first time through the synthesis of donor‐stabilised [SbF4]+ cations. In the presence of bidentate N‐donor ligands, SbF5 undergoes ligand‐induced autoionisation to yield robust [SbF4(L−L)]+ (L−L=2,2’bipyridine or 1,10‐phenanthroline) salts. DFT calculations and NBO analyses show strong Sb−N interactions that are necessary to stabilise the [SbF4]+ cation. |
doi_str_mv | 10.1002/chem.202103221 |
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The ability of the strong Lewis acid SbF5 to act as a fluoride‐ion donor has been demonstrated for the first time through the synthesis of donor‐stabilised [SbF4]+ cations. In the presence of bidentate N‐donor ligands, SbF5 undergoes ligand‐induced autoionisation to yield robust [SbF4(L−L)]+ (L−L=2,2’bipyridine or 1,10‐phenanthroline) salts. DFT calculations and NBO analyses show strong Sb−N interactions that are necessary to stabilise the [SbF4]+ cation.</description><identifier>ISSN: 0947-6539</identifier><identifier>EISSN: 1521-3765</identifier><identifier>DOI: 10.1002/chem.202103221</identifier><language>eng</language><subject>antimony ; cations ; DFT calculations ; fluorine ; Lewis acids</subject><ispartof>Chemistry : a European journal, 2021-11, Vol.27 (66), p.16334-16337</ispartof><rights>2021 Wiley‐VCH GmbH</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><orcidid>0000-0003-0821-089X</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://onlinelibrary.wiley.com/doi/pdf/10.1002%2Fchem.202103221$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fchem.202103221$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>315,781,785,1418,27926,27927,45576,45577</link.rule.ids></links><search><creatorcontrib>O'Donnell, Felix</creatorcontrib><creatorcontrib>Turnbull, Douglas</creatorcontrib><creatorcontrib>Wetmore, Stacey D.</creatorcontrib><creatorcontrib>Gerken, Michael</creatorcontrib><title>Donor‐Stabilised [SbF4]+: SbF5 as a Fluoride‐Ion Donor</title><title>Chemistry : a European journal</title><description>Antimony pentafluoride is a strong Lewis acid and fluoride‐ion acceptor that has not previously demonstrated any discreet fluoride‐ion donor properties. The first donor‐stabilised [SbF4]+ cations were prepared from the autoionisation of SbF5 in the presence of bidentate N‐donor ligands 2,2’‐bipyridine (bipy) and 1,10‐phenanthroline (phen) as their [SbF6]− salts. The [SbF4(N−N)][Sb2F11] (N−N=bipy, phen) salts were synthesised by the addition of one equivalent of SbF5⋅SO2 to [SbF4(N−N)][SbF6] in liquid SO2. The salts show remarkable stability and were characterised by Raman spectroscopy and multinuclear NMR spectroscopy. The crystal structures of [SbF4(phen)][SbF6] ⋅ 3CH3CN and [SbF4(phen)][SbF6] ⋅ 2SO2 were determined, showing distorted octahedral cations. DFT calculations and NBO analyses reveal that significant degree of electron‐pair donation from N to Sb stabilizes [SbF4]+ with the Sb−N bond strength being approximately two thirds of that of the Sb−F bonds in these cations and the cationic charge being primarily ligand‐centred.
The ability of the strong Lewis acid SbF5 to act as a fluoride‐ion donor has been demonstrated for the first time through the synthesis of donor‐stabilised [SbF4]+ cations. In the presence of bidentate N‐donor ligands, SbF5 undergoes ligand‐induced autoionisation to yield robust [SbF4(L−L)]+ (L−L=2,2’bipyridine or 1,10‐phenanthroline) salts. DFT calculations and NBO analyses show strong Sb−N interactions that are necessary to stabilise the [SbF4]+ cation.</description><subject>antimony</subject><subject>cations</subject><subject>DFT calculations</subject><subject>fluorine</subject><subject>Lewis acids</subject><issn>0947-6539</issn><issn>1521-3765</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2021</creationdate><recordtype>article</recordtype><recordid>eNo9kM1Kw0AUhQdRsFa3rrMUJHXu_N2kO4mtLVRcVFciwyS5wUh-aqZBuvMRfEafxNZKV4cD3zmLj7FL4CPgXNxkb1SPBBfApRBwxAagBYQSjT5mAx4rDI2W8Sk78_6dcx4bKQdsfNc2bffz9b1cu7SsSk958LJMp-r1ehxsUwfOBy6YVn3blTltwXnbBH-jc3ZSuMrTxX8O2fN08pTMwsXj_Ty5XYQrISMIFQcTOdQ6U4AQpVmKSKgIUpXrSOaRJpIIOlZcqUwgFgKwQOOckwRFLIfsav-76tqPnvza1qXPqKpcQ23vrdBojBZSiS0a79HPsqKNXXVl7bqNBW53huzOkD0Yssls8nBo8heumVr1</recordid><startdate>20211125</startdate><enddate>20211125</enddate><creator>O'Donnell, Felix</creator><creator>Turnbull, Douglas</creator><creator>Wetmore, Stacey D.</creator><creator>Gerken, Michael</creator><scope>7X8</scope><orcidid>https://orcid.org/0000-0003-0821-089X</orcidid></search><sort><creationdate>20211125</creationdate><title>Donor‐Stabilised [SbF4]+: SbF5 as a Fluoride‐Ion Donor</title><author>O'Donnell, Felix ; Turnbull, Douglas ; Wetmore, Stacey D. ; Gerken, Michael</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-p2381-40168a755c41718bcb77e74e1b4d583d85ee371594044c277f217f76aaa3e1f93</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2021</creationdate><topic>antimony</topic><topic>cations</topic><topic>DFT calculations</topic><topic>fluorine</topic><topic>Lewis acids</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>O'Donnell, Felix</creatorcontrib><creatorcontrib>Turnbull, Douglas</creatorcontrib><creatorcontrib>Wetmore, Stacey D.</creatorcontrib><creatorcontrib>Gerken, Michael</creatorcontrib><collection>MEDLINE - Academic</collection><jtitle>Chemistry : a European journal</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>O'Donnell, Felix</au><au>Turnbull, Douglas</au><au>Wetmore, Stacey D.</au><au>Gerken, Michael</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Donor‐Stabilised [SbF4]+: SbF5 as a Fluoride‐Ion Donor</atitle><jtitle>Chemistry : a European journal</jtitle><date>2021-11-25</date><risdate>2021</risdate><volume>27</volume><issue>66</issue><spage>16334</spage><epage>16337</epage><pages>16334-16337</pages><issn>0947-6539</issn><eissn>1521-3765</eissn><abstract>Antimony pentafluoride is a strong Lewis acid and fluoride‐ion acceptor that has not previously demonstrated any discreet fluoride‐ion donor properties. The first donor‐stabilised [SbF4]+ cations were prepared from the autoionisation of SbF5 in the presence of bidentate N‐donor ligands 2,2’‐bipyridine (bipy) and 1,10‐phenanthroline (phen) as their [SbF6]− salts. The [SbF4(N−N)][Sb2F11] (N−N=bipy, phen) salts were synthesised by the addition of one equivalent of SbF5⋅SO2 to [SbF4(N−N)][SbF6] in liquid SO2. The salts show remarkable stability and were characterised by Raman spectroscopy and multinuclear NMR spectroscopy. The crystal structures of [SbF4(phen)][SbF6] ⋅ 3CH3CN and [SbF4(phen)][SbF6] ⋅ 2SO2 were determined, showing distorted octahedral cations. DFT calculations and NBO analyses reveal that significant degree of electron‐pair donation from N to Sb stabilizes [SbF4]+ with the Sb−N bond strength being approximately two thirds of that of the Sb−F bonds in these cations and the cationic charge being primarily ligand‐centred.
The ability of the strong Lewis acid SbF5 to act as a fluoride‐ion donor has been demonstrated for the first time through the synthesis of donor‐stabilised [SbF4]+ cations. In the presence of bidentate N‐donor ligands, SbF5 undergoes ligand‐induced autoionisation to yield robust [SbF4(L−L)]+ (L−L=2,2’bipyridine or 1,10‐phenanthroline) salts. DFT calculations and NBO analyses show strong Sb−N interactions that are necessary to stabilise the [SbF4]+ cation.</abstract><doi>10.1002/chem.202103221</doi><tpages>4</tpages><orcidid>https://orcid.org/0000-0003-0821-089X</orcidid></addata></record> |
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subjects | antimony cations DFT calculations fluorine Lewis acids |
title | Donor‐Stabilised [SbF4]+: SbF5 as a Fluoride‐Ion Donor |
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