Facile and systematic access to the least-coordinating WCA [(RO)Al-F-Al(OR)] and its more Lewis-basic brother [F-Al(OR)] (R = C(CF))
By reaction of the Lewis acid Me 3 Si-F-Al(OR F ) 3 with a series of [PF 6 ] − salts, gaseous PF 5 and Me 3 Si-F are liberated and salts of the anion [F-Al(OR F ) 3 ] − ([f-al] − ; R F = C(CF 3 ) 3 ) can be obtained. By addition of another equivalent of Me 3 Si-F-Al(OR F ) 3 to [f-al] − , gaseous Me...
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| Veröffentlicht in: | Chemical science (Cambridge) 2018-09, Vol.9 (35), p.758-768 |
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| creator | Martens, Arthur Weis, Philippe Krummer, Michael Christian Kreuzer, Marvin Meierhöfer, Andreas Meier, Stefan C Bohnenberger, Jan Scherer, Harald Riddlestone, Ian Krossing, Ingo |
| description | By reaction of the Lewis acid Me
3
Si-F-Al(OR
F
)
3
with a series of [PF
6
]
−
salts, gaseous PF
5
and Me
3
Si-F are liberated and salts of the anion [F-Al(OR
F
)
3
]
−
([f-al]
−
; R
F
= C(CF
3
)
3
) can be obtained. By addition of another equivalent of Me
3
Si-F-Al(OR
F
)
3
to [f-al]
−
, gaseous Me
3
Si-F is released and salts of the least coordinating anion [(R
F
O)
3
Al-F-Al(OR
F
)
3
]
−
([al-f-al]
−
) are formed. Both procedures work for a series of synthetically useful cations including Ag
+
, [NO]
+
, [Ph
3
C]
+
and in very clean reactions with 5 g batch sizes giving excellent yields typically exceeding 90%. In addition, the synthesis of Me
3
Si-F-Al(OR
F
)
3
has been optimized and scaled up to 85 g batches in an one-pot procedure. These anions could previously only be obtained by difficult to control decomposition reactions of [Al(OR
F
)
4
]
−
or by halide abstraction reactions with Me
3
Si-F-Al(OR
F
)
3
, generating relatively large countercations that are unsuited for further use as universal starting materials. Especially [al-f-al]
−
is of interest for the stabilization of reactive cations, since it is even weaker coordinating than [Al(OR
F
)
4
]
−
and more stable against strong electrophiles. This bridged anion can be seen as an adduct of [f-al]
−
and Al(OR
F
)
3
. Thus, it is similarly Lewis acidic as BF
3
and eventually reacts with nucleophiles (Nu) from the reaction environment to yield Nu-Al(OR
F
)
3
and [f-al]
−
. This prevents working with [al-f-al]
−
salts in ethereal or other donor solvents. By contrast, the [f-al]
−
anion is no longer Lewis acidic and may therefore be used for reactions involving stronger nucleophiles than the [al-f-al]
−
anion can withstand. Subsequently it may be transformed into the [al-f-al]
−
salt by simple addition of one equivalent of Me
3
Si-F-Al(OR
F
)
3
.
The least-coordinating anion [(R
F
O)
3
Al-F-Al(OR
F
)
3
]
−
and its more Lewis-basic brother [F-Al(OR
F
)
3
]
−
(R
F
= C(CF
3
)
3
). |
| doi_str_mv | 10.1039/c8sc02591f |
| format | Article |
| fullrecord | <record><control><sourceid>rsc</sourceid><recordid>TN_cdi_rsc_primary_c8sc02591f</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>c8sc02591f</sourcerecordid><originalsourceid>FETCH-LOGICAL-r107t-c31ad0198b58335e55516f554aec34cf519e117976031f0233b0570a6e94e48f3</originalsourceid><addsrcrecordid>eNpFkEFLw0AQhRdRsNRevAt7TA6ru5lskj14CMGoUCgExUORstlMNJI2shOQ3vvDDSr2Xd7Ae3wMj7FLJa-VBHPjMnIy0ka1J2wWyViJRIM5_b8jec4WRB9yEoDSUTpjh9K6rkdudw2nPY24tWPnuHUOifg48PEdeY-WRuGGwTfdbsp3b_ylyPk6qFZh3otS5H2wqsLXH0o3Et8OHvkSvzoStaWJV_thAnm-PnaDit_yIijKMLxgZ63tCRd_PmfP5d1T8SCWq_vHIl8Kr2Q6PQDKNlKZrNYZgEattUparWOLDmLXamVQqdSkiQTVygigljqVNkETY5y1MGdXv1xPbvPpu631-81xNfgGY5Fbvw</addsrcrecordid><sourcetype>Publisher</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype></control><display><type>article</type><title>Facile and systematic access to the least-coordinating WCA [(RO)Al-F-Al(OR)] and its more Lewis-basic brother [F-Al(OR)] (R = C(CF))</title><source>PubMed Central</source><source>Directory of Open Access Journals</source><source>EZB Electronic Journals Library</source><source>PubMed Central Open Access</source><creator>Martens, Arthur ; Weis, Philippe ; Krummer, Michael Christian ; Kreuzer, Marvin ; Meierhöfer, Andreas ; Meier, Stefan C ; Bohnenberger, Jan ; Scherer, Harald ; Riddlestone, Ian ; Krossing, Ingo</creator><creatorcontrib>Martens, Arthur ; Weis, Philippe ; Krummer, Michael Christian ; Kreuzer, Marvin ; Meierhöfer, Andreas ; Meier, Stefan C ; Bohnenberger, Jan ; Scherer, Harald ; Riddlestone, Ian ; Krossing, Ingo</creatorcontrib><description>By reaction of the Lewis acid Me
3
Si-F-Al(OR
F
)
3
with a series of [PF
6
]
−
salts, gaseous PF
5
and Me
3
Si-F are liberated and salts of the anion [F-Al(OR
F
)
3
]
−
([f-al]
−
; R
F
= C(CF
3
)
3
) can be obtained. By addition of another equivalent of Me
3
Si-F-Al(OR
F
)
3
to [f-al]
−
, gaseous Me
3
Si-F is released and salts of the least coordinating anion [(R
F
O)
3
Al-F-Al(OR
F
)
3
]
−
([al-f-al]
−
) are formed. Both procedures work for a series of synthetically useful cations including Ag
+
, [NO]
+
, [Ph
3
C]
+
and in very clean reactions with 5 g batch sizes giving excellent yields typically exceeding 90%. In addition, the synthesis of Me
3
Si-F-Al(OR
F
)
3
has been optimized and scaled up to 85 g batches in an one-pot procedure. These anions could previously only be obtained by difficult to control decomposition reactions of [Al(OR
F
)
4
]
−
or by halide abstraction reactions with Me
3
Si-F-Al(OR
F
)
3
, generating relatively large countercations that are unsuited for further use as universal starting materials. Especially [al-f-al]
−
is of interest for the stabilization of reactive cations, since it is even weaker coordinating than [Al(OR
F
)
4
]
−
and more stable against strong electrophiles. This bridged anion can be seen as an adduct of [f-al]
−
and Al(OR
F
)
3
. Thus, it is similarly Lewis acidic as BF
3
and eventually reacts with nucleophiles (Nu) from the reaction environment to yield Nu-Al(OR
F
)
3
and [f-al]
−
. This prevents working with [al-f-al]
−
salts in ethereal or other donor solvents. By contrast, the [f-al]
−
anion is no longer Lewis acidic and may therefore be used for reactions involving stronger nucleophiles than the [al-f-al]
−
anion can withstand. Subsequently it may be transformed into the [al-f-al]
−
salt by simple addition of one equivalent of Me
3
Si-F-Al(OR
F
)
3
.
The least-coordinating anion [(R
F
O)
3
Al-F-Al(OR
F
)
3
]
−
and its more Lewis-basic brother [F-Al(OR
F
)
3
]
−
(R
F
= C(CF
3
)
3
).</description><identifier>ISSN: 2041-6520</identifier><identifier>EISSN: 2041-6539</identifier><identifier>DOI: 10.1039/c8sc02591f</identifier><language>eng</language><ispartof>Chemical science (Cambridge), 2018-09, Vol.9 (35), p.758-768</ispartof><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,776,780,860,27901,27902</link.rule.ids></links><search><creatorcontrib>Martens, Arthur</creatorcontrib><creatorcontrib>Weis, Philippe</creatorcontrib><creatorcontrib>Krummer, Michael Christian</creatorcontrib><creatorcontrib>Kreuzer, Marvin</creatorcontrib><creatorcontrib>Meierhöfer, Andreas</creatorcontrib><creatorcontrib>Meier, Stefan C</creatorcontrib><creatorcontrib>Bohnenberger, Jan</creatorcontrib><creatorcontrib>Scherer, Harald</creatorcontrib><creatorcontrib>Riddlestone, Ian</creatorcontrib><creatorcontrib>Krossing, Ingo</creatorcontrib><title>Facile and systematic access to the least-coordinating WCA [(RO)Al-F-Al(OR)] and its more Lewis-basic brother [F-Al(OR)] (R = C(CF))</title><title>Chemical science (Cambridge)</title><description>By reaction of the Lewis acid Me
3
Si-F-Al(OR
F
)
3
with a series of [PF
6
]
−
salts, gaseous PF
5
and Me
3
Si-F are liberated and salts of the anion [F-Al(OR
F
)
3
]
−
([f-al]
−
; R
F
= C(CF
3
)
3
) can be obtained. By addition of another equivalent of Me
3
Si-F-Al(OR
F
)
3
to [f-al]
−
, gaseous Me
3
Si-F is released and salts of the least coordinating anion [(R
F
O)
3
Al-F-Al(OR
F
)
3
]
−
([al-f-al]
−
) are formed. Both procedures work for a series of synthetically useful cations including Ag
+
, [NO]
+
, [Ph
3
C]
+
and in very clean reactions with 5 g batch sizes giving excellent yields typically exceeding 90%. In addition, the synthesis of Me
3
Si-F-Al(OR
F
)
3
has been optimized and scaled up to 85 g batches in an one-pot procedure. These anions could previously only be obtained by difficult to control decomposition reactions of [Al(OR
F
)
4
]
−
or by halide abstraction reactions with Me
3
Si-F-Al(OR
F
)
3
, generating relatively large countercations that are unsuited for further use as universal starting materials. Especially [al-f-al]
−
is of interest for the stabilization of reactive cations, since it is even weaker coordinating than [Al(OR
F
)
4
]
−
and more stable against strong electrophiles. This bridged anion can be seen as an adduct of [f-al]
−
and Al(OR
F
)
3
. Thus, it is similarly Lewis acidic as BF
3
and eventually reacts with nucleophiles (Nu) from the reaction environment to yield Nu-Al(OR
F
)
3
and [f-al]
−
. This prevents working with [al-f-al]
−
salts in ethereal or other donor solvents. By contrast, the [f-al]
−
anion is no longer Lewis acidic and may therefore be used for reactions involving stronger nucleophiles than the [al-f-al]
−
anion can withstand. Subsequently it may be transformed into the [al-f-al]
−
salt by simple addition of one equivalent of Me
3
Si-F-Al(OR
F
)
3
.
The least-coordinating anion [(R
F
O)
3
Al-F-Al(OR
F
)
3
]
−
and its more Lewis-basic brother [F-Al(OR
F
)
3
]
−
(R
F
= C(CF
3
)
3
).</description><issn>2041-6520</issn><issn>2041-6539</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2018</creationdate><recordtype>article</recordtype><sourceid/><recordid>eNpFkEFLw0AQhRdRsNRevAt7TA6ru5lskj14CMGoUCgExUORstlMNJI2shOQ3vvDDSr2Xd7Ae3wMj7FLJa-VBHPjMnIy0ka1J2wWyViJRIM5_b8jec4WRB9yEoDSUTpjh9K6rkdudw2nPY24tWPnuHUOifg48PEdeY-WRuGGwTfdbsp3b_ylyPk6qFZh3otS5H2wqsLXH0o3Et8OHvkSvzoStaWJV_thAnm-PnaDit_yIijKMLxgZ63tCRd_PmfP5d1T8SCWq_vHIl8Kr2Q6PQDKNlKZrNYZgEattUparWOLDmLXamVQqdSkiQTVygigljqVNkETY5y1MGdXv1xPbvPpu631-81xNfgGY5Fbvw</recordid><startdate>20180921</startdate><enddate>20180921</enddate><creator>Martens, Arthur</creator><creator>Weis, Philippe</creator><creator>Krummer, Michael Christian</creator><creator>Kreuzer, Marvin</creator><creator>Meierhöfer, Andreas</creator><creator>Meier, Stefan C</creator><creator>Bohnenberger, Jan</creator><creator>Scherer, Harald</creator><creator>Riddlestone, Ian</creator><creator>Krossing, Ingo</creator><scope/></search><sort><creationdate>20180921</creationdate><title>Facile and systematic access to the least-coordinating WCA [(RO)Al-F-Al(OR)] and its more Lewis-basic brother [F-Al(OR)] (R = C(CF))</title><author>Martens, Arthur ; Weis, Philippe ; Krummer, Michael Christian ; Kreuzer, Marvin ; Meierhöfer, Andreas ; Meier, Stefan C ; Bohnenberger, Jan ; Scherer, Harald ; Riddlestone, Ian ; Krossing, Ingo</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-r107t-c31ad0198b58335e55516f554aec34cf519e117976031f0233b0570a6e94e48f3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2018</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Martens, Arthur</creatorcontrib><creatorcontrib>Weis, Philippe</creatorcontrib><creatorcontrib>Krummer, Michael Christian</creatorcontrib><creatorcontrib>Kreuzer, Marvin</creatorcontrib><creatorcontrib>Meierhöfer, Andreas</creatorcontrib><creatorcontrib>Meier, Stefan C</creatorcontrib><creatorcontrib>Bohnenberger, Jan</creatorcontrib><creatorcontrib>Scherer, Harald</creatorcontrib><creatorcontrib>Riddlestone, Ian</creatorcontrib><creatorcontrib>Krossing, Ingo</creatorcontrib><jtitle>Chemical science (Cambridge)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Martens, Arthur</au><au>Weis, Philippe</au><au>Krummer, Michael Christian</au><au>Kreuzer, Marvin</au><au>Meierhöfer, Andreas</au><au>Meier, Stefan C</au><au>Bohnenberger, Jan</au><au>Scherer, Harald</au><au>Riddlestone, Ian</au><au>Krossing, Ingo</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Facile and systematic access to the least-coordinating WCA [(RO)Al-F-Al(OR)] and its more Lewis-basic brother [F-Al(OR)] (R = C(CF))</atitle><jtitle>Chemical science (Cambridge)</jtitle><date>2018-09-21</date><risdate>2018</risdate><volume>9</volume><issue>35</issue><spage>758</spage><epage>768</epage><pages>758-768</pages><issn>2041-6520</issn><eissn>2041-6539</eissn><abstract>By reaction of the Lewis acid Me
3
Si-F-Al(OR
F
)
3
with a series of [PF
6
]
−
salts, gaseous PF
5
and Me
3
Si-F are liberated and salts of the anion [F-Al(OR
F
)
3
]
−
([f-al]
−
; R
F
= C(CF
3
)
3
) can be obtained. By addition of another equivalent of Me
3
Si-F-Al(OR
F
)
3
to [f-al]
−
, gaseous Me
3
Si-F is released and salts of the least coordinating anion [(R
F
O)
3
Al-F-Al(OR
F
)
3
]
−
([al-f-al]
−
) are formed. Both procedures work for a series of synthetically useful cations including Ag
+
, [NO]
+
, [Ph
3
C]
+
and in very clean reactions with 5 g batch sizes giving excellent yields typically exceeding 90%. In addition, the synthesis of Me
3
Si-F-Al(OR
F
)
3
has been optimized and scaled up to 85 g batches in an one-pot procedure. These anions could previously only be obtained by difficult to control decomposition reactions of [Al(OR
F
)
4
]
−
or by halide abstraction reactions with Me
3
Si-F-Al(OR
F
)
3
, generating relatively large countercations that are unsuited for further use as universal starting materials. Especially [al-f-al]
−
is of interest for the stabilization of reactive cations, since it is even weaker coordinating than [Al(OR
F
)
4
]
−
and more stable against strong electrophiles. This bridged anion can be seen as an adduct of [f-al]
−
and Al(OR
F
)
3
. Thus, it is similarly Lewis acidic as BF
3
and eventually reacts with nucleophiles (Nu) from the reaction environment to yield Nu-Al(OR
F
)
3
and [f-al]
−
. This prevents working with [al-f-al]
−
salts in ethereal or other donor solvents. By contrast, the [f-al]
−
anion is no longer Lewis acidic and may therefore be used for reactions involving stronger nucleophiles than the [al-f-al]
−
anion can withstand. Subsequently it may be transformed into the [al-f-al]
−
salt by simple addition of one equivalent of Me
3
Si-F-Al(OR
F
)
3
.
The least-coordinating anion [(R
F
O)
3
Al-F-Al(OR
F
)
3
]
−
and its more Lewis-basic brother [F-Al(OR
F
)
3
]
−
(R
F
= C(CF
3
)
3
).</abstract><doi>10.1039/c8sc02591f</doi><tpages>11</tpages><oa>free_for_read</oa></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 2041-6520 |
| ispartof | Chemical science (Cambridge), 2018-09, Vol.9 (35), p.758-768 |
| issn | 2041-6520 2041-6539 |
| language | eng |
| recordid | cdi_rsc_primary_c8sc02591f |
| source | PubMed Central; Directory of Open Access Journals; EZB Electronic Journals Library; PubMed Central Open Access |
| title | Facile and systematic access to the least-coordinating WCA [(RO)Al-F-Al(OR)] and its more Lewis-basic brother [F-Al(OR)] (R = C(CF)) |
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