Synthesis and Characterization of 2‐Mono‐ and 1,2‐Diaminocarba‐closo‐dodecaborates M[1‐R‐2‐H2N‐closo‐CB11H10] (R=H, Ph, H2N, CyHN)
Identifieur interne : 001154 ( Main/Exploration ); précédent : 001153; suivant : 001155Synthesis and Characterization of 2‐Mono‐ and 1,2‐Diaminocarba‐closo‐dodecaborates M[1‐R‐2‐H2N‐closo‐CB11H10] (R=H, Ph, H2N, CyHN)
Auteurs : Maik Finze [Allemagne]Source :
- Chemistry – A European Journal [ 0947-6539 ] ; 2009-01-12.
Abstract
The first primary 2‐aminocarba‐closo‐dodecaborates [1‐R‐2‐H2N‐closo‐CB11H10]− (R=H (1), Ph (2)) have been synthesized by insertion reactions of (Me3Si)2NBCl2 into the trianions [7‐R‐7‐nido‐CB10H10]3−. The difunctionalized species [1,2‐(H2N)2‐closo‐CB11H10] (3) and 1‐CyHN‐2‐H3N‐closo‐CB11H10 (H‐4) have been prepared analogously from (Me3Si)2NBCl2 and 7‐H3N‐7‐nido‐CB10H12. In addition, the preparation of [Et4N][1‐H2N‐2‐Ph‐closo‐CB11H10] ([Et4N]‐5) starting from PhBCl2 and 7‐H3N‐7‐nido‐CB10H12 is described. Methylation of the [1‐Ph‐2‐H2N‐closo‐CB11H10]− ion (2) to produce 1‐Ph‐2‐Me3N‐closo‐CB11H10 (6) is reported. The crystal structures of [Et4N]‐2, [Et4N]‐5, and 6 were determined and the geometric parameters were compared to theoretical values derived from DFT and ab initio calculations. All new compounds were studied by NMR, IR, and Raman spectroscopy, MALDI mass spectrometry, and elemental analysis. The discussion of the experimental NMR chemical shifts and of selected vibrational band positions is supported by theoretical data. The thermal properties were investigated by differential scanning calorimetry (DSC). The pKa values of 2‐H3N‐closo‐CB11H11 (H‐1), 1‐H3N‐closo‐CB11H10 (H‐7), and 1,2‐(H3N)2‐closo‐CB11H10 (H2‐3) were determined by potentiometric titration and by NMR studies. The experimental results are compared to theoretical data (DFT and ab initio). The basicities of the aminocarba‐closo‐dodecaborates agree well with the spectroscopic and structural properties.
Functionalized carba‐closo‐dodecaborates: Carba‐closo‐dodecaborate anions with primary amino substituents bonded to the boron atom in the 2‐position: [1‐R‐2‐H2N‐closo‐CB11H10]− (R=H, Ph, H2N, CyHN) have been synthesized and characterized by spectroscopic and structural methods (see picture). The pKa values of the corresponding protonated carboranes were studied and compared to those of 1‐H3N‐closo‐CB11H11.
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DOI: 10.1002/chem.200801497
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<record><TEI wicri:istexFullTextTei="biblStruct"><teiHeader><fileDesc><titleStmt><title xml:lang="en">Synthesis and Characterization of 2‐Mono‐ and 1,2‐Diaminocarba‐closo‐dodecaborates M[1‐R‐2‐H2N‐closo‐CB11H10] (R=H, Ph, H2N, CyHN)</title><author><name sortKey="Finze, Maik" sort="Finze, Maik" uniqKey="Finze M" first="Maik" last="Finze">Maik Finze</name></author></titleStmt><publicationStmt><idno type="wicri:source">ISTEX</idno><idno type="RBID">ISTEX:0AB8164E09B052F5F7FB8E374DAA59B83C72F702</idno><date when="2009" year="2009">2009</date><idno type="doi">10.1002/chem.200801497</idno><idno type="url">https://api.istex.fr/ark:/67375/WNG-XC8PDQ8F-B/fulltext.pdf</idno><idno type="wicri:Area/Istex/Corpus">001775</idno><idno type="wicri:explorRef" wicri:stream="Istex" wicri:step="Corpus" wicri:corpus="ISTEX">001775</idno><idno type="wicri:Area/Istex/Curation">001775</idno><idno type="wicri:Area/Istex/Checkpoint">000272</idno><idno type="wicri:explorRef" wicri:stream="Istex" wicri:step="Checkpoint">000272</idno><idno type="wicri:doubleKey">0947-6539:2009:Finze M:synthesis:and:characterization</idno><idno type="wicri:Area/Main/Merge">001164</idno><idno type="wicri:Area/Main/Curation">001154</idno><idno type="wicri:Area/Main/Exploration">001154</idno></publicationStmt><sourceDesc><biblStruct><analytic><title level="a" type="main">Synthesis and Characterization of 2‐Mono‐ and 1,2‐Diaminocarba‐closo‐dodecaborates M[1‐R‐2‐H2N‐closo‐CB11H10] (R=H, Ph, H2N, CyHN)</title><author><name sortKey="Finze, Maik" sort="Finze, Maik" uniqKey="Finze M" first="Maik" last="Finze">Maik Finze</name><affiliation></affiliation><affiliation wicri:level="1"><country wicri:rule="url">Allemagne</country></affiliation></author></analytic><monogr></monogr><series><title level="j" type="main">Chemistry – A European Journal</title><title level="j" type="alt">CHEMISTRY - A EUROPEAN JOURNAL</title><idno type="ISSN">0947-6539</idno><idno type="eISSN">1521-3765</idno><imprint><biblScope unit="vol">15</biblScope><biblScope unit="issue">4</biblScope><biblScope unit="page" from="947">947</biblScope><biblScope unit="page" to="962">962</biblScope><biblScope unit="page-count">16</biblScope><publisher>WILEY‐VCH Verlag</publisher><pubPlace>Weinheim</pubPlace><date type="published" when="2009-01-12">2009-01-12</date></imprint><idno type="ISSN">0947-6539</idno></series></biblStruct></sourceDesc><seriesStmt><idno type="ISSN">0947-6539</idno></seriesStmt></fileDesc><profileDesc><textClass></textClass></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">The first primary 2‐aminocarba‐closo‐dodecaborates [1‐R‐2‐H2N‐closo‐CB11H10]− (R=H (1), Ph (2)) have been synthesized by insertion reactions of (Me3Si)2NBCl2 into the trianions [7‐R‐7‐nido‐CB10H10]3−. The difunctionalized species [1,2‐(H2N)2‐closo‐CB11H10] (3) and 1‐CyHN‐2‐H3N‐closo‐CB11H10 (H‐4) have been prepared analogously from (Me3Si)2NBCl2 and 7‐H3N‐7‐nido‐CB10H12. In addition, the preparation of [Et4N][1‐H2N‐2‐Ph‐closo‐CB11H10] ([Et4N]‐5) starting from PhBCl2 and 7‐H3N‐7‐nido‐CB10H12 is described. Methylation of the [1‐Ph‐2‐H2N‐closo‐CB11H10]− ion (2) to produce 1‐Ph‐2‐Me3N‐closo‐CB11H10 (6) is reported. The crystal structures of [Et4N]‐2, [Et4N]‐5, and 6 were determined and the geometric parameters were compared to theoretical values derived from DFT and ab initio calculations. All new compounds were studied by NMR, IR, and Raman spectroscopy, MALDI mass spectrometry, and elemental analysis. The discussion of the experimental NMR chemical shifts and of selected vibrational band positions is supported by theoretical data. The thermal properties were investigated by differential scanning calorimetry (DSC). The pKa values of 2‐H3N‐closo‐CB11H11 (H‐1), 1‐H3N‐closo‐CB11H10 (H‐7), and 1,2‐(H3N)2‐closo‐CB11H10 (H2‐3) were determined by potentiometric titration and by NMR studies. The experimental results are compared to theoretical data (DFT and ab initio). The basicities of the aminocarba‐closo‐dodecaborates agree well with the spectroscopic and structural properties.</div><div type="abstract" xml:lang="en">Functionalized carba‐closo‐dodecaborates: Carba‐closo‐dodecaborate anions with primary amino substituents bonded to the boron atom in the 2‐position: [1‐R‐2‐H2N‐closo‐CB11H10]− (R=H, Ph, H2N, CyHN) have been synthesized and characterized by spectroscopic and structural methods (see picture). The pKa values of the corresponding protonated carboranes were studied and compared to those of 1‐H3N‐closo‐CB11H11.</div></front></TEI><affiliations><list><country><li>Allemagne</li></country></list><tree><country name="Allemagne"><noRegion><name sortKey="Finze, Maik" sort="Finze, Maik" uniqKey="Finze M" first="Maik" last="Finze">Maik Finze</name></noRegion></country></tree></affiliations></record>Pour manipuler ce document sous Unix (Dilib)
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