Nucleophilic addition and substitution at coordinatively saturated boron by facile 1,2-hydrogen shuttling onto a carbene donorElectronic supplementary information (ESI) available: General experimental details, characterization data for all reported compounds and details of the DFT calculations. CCDC 1563216-1563221. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc03193a

The reaction of [(cAAC Me )BH 3 ] (cAAC Me = 1-(2,6- i Pr 2 C 6 H 3 )-3,3,5,5-tetramethylpyrrolidin-2-ylidene) with a range of organolithium compounds led to the exclusive formation of the corresponding (dihydro)organoborates, Li + [(cAAC Me H)BH 2 R] − (R = sp 3 -, sp 2 -, or sp-hybridised organic...

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Main Authors: Auerhammer, Dominic, Arrowsmith, Merle, Braunschweig, Holger, Dewhurst, Rian D, Jiménez-Halla, J. Oscar C, Kupfer, Thomas
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Jiménez-Halla, J. Oscar C
Kupfer, Thomas
description The reaction of [(cAAC Me )BH 3 ] (cAAC Me = 1-(2,6- i Pr 2 C 6 H 3 )-3,3,5,5-tetramethylpyrrolidin-2-ylidene) with a range of organolithium compounds led to the exclusive formation of the corresponding (dihydro)organoborates, Li + [(cAAC Me H)BH 2 R] − (R = sp 3 -, sp 2 -, or sp-hybridised organic substituent), by migration of one boron-bound hydrogen atom to the adjacent carbene carbon of the cAAC ligand. A subsequent deprotonation/salt metathesis reaction with Me 3 SiCl or spontaneous LiH elimination yielded the neutral cAAC-supported mono(organo)boranes, [(cAAC Me )BH 2 R]. Similarly the reaction of [(cAAC Me )BH 3 ] with a neutral donor base L resulted in adduct formation by shuttling one boron-bound hydrogen to the cAAC ligand, to generate [(cAAC Me H)BH 2 L], either irreversibly (L = cAAC Me ) or reversibly (L = pyridine). Variable-temperature NMR data and DFT calculations on [(cAAC Me H)BH 2 (cAAC Me )] show that the hydrogen on the former carbene carbon atom exchanges rapidly with the boron-bound hydrides. Anionic organic sp 3 -, sp 2 - and sp-nucleophiles as well as neutral Lewis bases were shown to add to a coordinatively saturated cyclic (alkyl)(amino)carbene (cAAC) supported borane thanks to reversible transfer of a hydrogen atom from boron to the adjacent Lewis acidic cAAC carbene carbon atom.
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A subsequent deprotonation/salt metathesis reaction with Me 3 SiCl or spontaneous LiH elimination yielded the neutral cAAC-supported mono(organo)boranes, [(cAAC Me )BH 2 R]. Similarly the reaction of [(cAAC Me )BH 3 ] with a neutral donor base L resulted in adduct formation by shuttling one boron-bound hydrogen to the cAAC ligand, to generate [(cAAC Me H)BH 2 L], either irreversibly (L = cAAC Me ) or reversibly (L = pyridine). Variable-temperature NMR data and DFT calculations on [(cAAC Me H)BH 2 (cAAC Me )] show that the hydrogen on the former carbene carbon atom exchanges rapidly with the boron-bound hydrides. Anionic organic sp 3 -, sp 2 - and sp-nucleophiles as well as neutral Lewis bases were shown to add to a coordinatively saturated cyclic (alkyl)(amino)carbene (cAAC) supported borane thanks to reversible transfer of a hydrogen atom from boron to the adjacent Lewis acidic cAAC carbene carbon atom.</description><identifier>ISSN: 2041-6520</identifier><identifier>EISSN: 2041-6539</identifier><identifier>DOI: 10.1039/c7sc03193a</identifier><language>eng</language><creationdate>2017-09</creationdate><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>315,786,790,27957,27958</link.rule.ids></links><search><creatorcontrib>Auerhammer, Dominic</creatorcontrib><creatorcontrib>Arrowsmith, Merle</creatorcontrib><creatorcontrib>Braunschweig, Holger</creatorcontrib><creatorcontrib>Dewhurst, Rian D</creatorcontrib><creatorcontrib>Jiménez-Halla, J. Oscar C</creatorcontrib><creatorcontrib>Kupfer, Thomas</creatorcontrib><title>Nucleophilic addition and substitution at coordinatively saturated boron by facile 1,2-hydrogen shuttling onto a carbene donorElectronic supplementary information (ESI) available: General experimental details, characterization data for all reported compounds and details of the DFT calculations. CCDC 1563216-1563221. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc03193a</title><description>The reaction of [(cAAC Me )BH 3 ] (cAAC Me = 1-(2,6- i Pr 2 C 6 H 3 )-3,3,5,5-tetramethylpyrrolidin-2-ylidene) with a range of organolithium compounds led to the exclusive formation of the corresponding (dihydro)organoborates, Li + [(cAAC Me H)BH 2 R] − (R = sp 3 -, sp 2 -, or sp-hybridised organic substituent), by migration of one boron-bound hydrogen atom to the adjacent carbene carbon of the cAAC ligand. A subsequent deprotonation/salt metathesis reaction with Me 3 SiCl or spontaneous LiH elimination yielded the neutral cAAC-supported mono(organo)boranes, [(cAAC Me )BH 2 R]. Similarly the reaction of [(cAAC Me )BH 3 ] with a neutral donor base L resulted in adduct formation by shuttling one boron-bound hydrogen to the cAAC ligand, to generate [(cAAC Me H)BH 2 L], either irreversibly (L = cAAC Me ) or reversibly (L = pyridine). Variable-temperature NMR data and DFT calculations on [(cAAC Me H)BH 2 (cAAC Me )] show that the hydrogen on the former carbene carbon atom exchanges rapidly with the boron-bound hydrides. Anionic organic sp 3 -, sp 2 - and sp-nucleophiles as well as neutral Lewis bases were shown to add to a coordinatively saturated cyclic (alkyl)(amino)carbene (cAAC) supported borane thanks to reversible transfer of a hydrogen atom from boron to the adjacent Lewis acidic cAAC carbene carbon atom.</description><issn>2041-6520</issn><issn>2041-6539</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2017</creationdate><recordtype>article</recordtype><sourceid/><recordid>eNqFUcFuEzEQ3SKQqEov3JGGG5WasF43qdLrNim5wIHeo1l7Nmvk2Kuxt2L5F_61001FD0jgy1ie9968Ny6K96qcq1KvPpvrZEqtVhpfFadVeaVmy4Vevf5zr8q3xXlKP0o5WqtFdX168vvrYDzFvnPeGUBrXXYxAAYLaWhSdnk4PmQwMbJ1AbN7ID9CwjwwZrLQRBZEM0KLxnkCdVnNutFy3FOA1A05exf2EEOOgGCQGwoENobIa08mC1tmp6HvPR0oZOQRXGgjH3Ca_Wn9fXsB-IDOY-PpBu6Ez-iBfvbEbqJ4sJQFkC7BdMhosnR-HfkWM4LIAXoPTH3kJ9cmHvo4BJumsM9siC3kjuB2cy9GvRn8JJHmUNe3NajFUldqOZtqpeawEVVxN0kYHpMY8XHPKPs0x7kuQL3dgOCiCDPQS-JjQkgk875tb-Dvf3xXvGnRJzp_rmfFh836vv4y42R2vUSXVe1e4Pqs-Piv_q63rf6fxiO-CcFr</recordid><startdate>20170925</startdate><enddate>20170925</enddate><creator>Auerhammer, Dominic</creator><creator>Arrowsmith, Merle</creator><creator>Braunschweig, Holger</creator><creator>Dewhurst, Rian D</creator><creator>Jiménez-Halla, J. 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Oscar C ; Kupfer, Thomas</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-rsc_primary_c7sc03193a3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2017</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Auerhammer, Dominic</creatorcontrib><creatorcontrib>Arrowsmith, Merle</creatorcontrib><creatorcontrib>Braunschweig, Holger</creatorcontrib><creatorcontrib>Dewhurst, Rian D</creatorcontrib><creatorcontrib>Jiménez-Halla, J. Oscar C</creatorcontrib><creatorcontrib>Kupfer, Thomas</creatorcontrib></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Auerhammer, Dominic</au><au>Arrowsmith, Merle</au><au>Braunschweig, Holger</au><au>Dewhurst, Rian D</au><au>Jiménez-Halla, J. Oscar C</au><au>Kupfer, Thomas</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Nucleophilic addition and substitution at coordinatively saturated boron by facile 1,2-hydrogen shuttling onto a carbene donorElectronic supplementary information (ESI) available: General experimental details, characterization data for all reported compounds and details of the DFT calculations. CCDC 1563216-1563221. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc03193a</atitle><date>2017-09-25</date><risdate>2017</risdate><volume>8</volume><issue>1</issue><spage>766</spage><epage>771</epage><pages>766-771</pages><issn>2041-6520</issn><eissn>2041-6539</eissn><notes>For ESI and crystallographic data in CIF or other electronic format see DOI</notes><notes>Electronic supplementary information (ESI) available: General experimental details, characterization data for all reported compounds and details of the DFT calculations. CCDC</notes><notes>10.1039/c7sc03193a</notes><notes>1563216-1563221</notes><abstract>The reaction of [(cAAC Me )BH 3 ] (cAAC Me = 1-(2,6- i Pr 2 C 6 H 3 )-3,3,5,5-tetramethylpyrrolidin-2-ylidene) with a range of organolithium compounds led to the exclusive formation of the corresponding (dihydro)organoborates, Li + [(cAAC Me H)BH 2 R] − (R = sp 3 -, sp 2 -, or sp-hybridised organic substituent), by migration of one boron-bound hydrogen atom to the adjacent carbene carbon of the cAAC ligand. A subsequent deprotonation/salt metathesis reaction with Me 3 SiCl or spontaneous LiH elimination yielded the neutral cAAC-supported mono(organo)boranes, [(cAAC Me )BH 2 R]. Similarly the reaction of [(cAAC Me )BH 3 ] with a neutral donor base L resulted in adduct formation by shuttling one boron-bound hydrogen to the cAAC ligand, to generate [(cAAC Me H)BH 2 L], either irreversibly (L = cAAC Me ) or reversibly (L = pyridine). Variable-temperature NMR data and DFT calculations on [(cAAC Me H)BH 2 (cAAC Me )] show that the hydrogen on the former carbene carbon atom exchanges rapidly with the boron-bound hydrides. Anionic organic sp 3 -, sp 2 - and sp-nucleophiles as well as neutral Lewis bases were shown to add to a coordinatively saturated cyclic (alkyl)(amino)carbene (cAAC) supported borane thanks to reversible transfer of a hydrogen atom from boron to the adjacent Lewis acidic cAAC carbene carbon atom.</abstract><doi>10.1039/c7sc03193a</doi><tpages>6</tpages></addata></record>
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title Nucleophilic addition and substitution at coordinatively saturated boron by facile 1,2-hydrogen shuttling onto a carbene donorElectronic supplementary information (ESI) available: General experimental details, characterization data for all reported compounds and details of the DFT calculations. CCDC 1563216-1563221. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc03193a
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