Nucleophilic Addition Reactions to 10-Acetonitrilium Derivative of <i>nido</i>-Carborane and Intramolecular NH⋯HB Interactions in <i>N</i>-Alkyl Amidines 10-RNHC(Me)=NH-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub>
The addition reactions of water, alcohols, and primary and secondary amines to the 10-acetonitrilium derivative of <i>nido</i>-carborane were studied. Hydrolysis of 10-MeC≡N-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub> results in iminol 10-MeC(OH)=HN-7...
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2025-02-01
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| author | Kirill R. Pakholkov Ekaterina V. Bogdanova Marina Yu. Stogniy Kyrill Yu. Suponitsky Sergey A. Anufriev Igor B. Sivaev Vladimir I. Bregadze |
| author_facet | Kirill R. Pakholkov Ekaterina V. Bogdanova Marina Yu. Stogniy Kyrill Yu. Suponitsky Sergey A. Anufriev Igor B. Sivaev Vladimir I. Bregadze |
| author_sort | Kirill R. Pakholkov |
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| description | The addition reactions of water, alcohols, and primary and secondary amines to the 10-acetonitrilium derivative of <i>nido</i>-carborane were studied. Hydrolysis of 10-MeC≡N-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub> results in iminol 10-MeC(OH)=HN-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub>, which, on treatment with a base, gives amide [10-MeC(=O)HN-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub>]<sup>−</sup>. The reactions of 10-MeC≡N-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub> with alcohols lead to imidates 10-ROC(Me)=HN-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub> (R = Me, Et) as mixtures of <i>E</i>- and <i>Z</i>-isomers. In the solid state, 10-MeOC(Me)=HN-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub> adopts <i>E</i>-configuration. The reactions of 10-MeC≡N-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub> with primary amines result in amidines 10-RNHC(Me)=HN-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub> (R = Me, Et) as mixtures of <i>E</i>- and <i>Z</i>-isomers. In the solid state 10-EtNHC(Me)=HN-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub> was found to have the <i>Z</i>-configuration, which is stabilized by intramolecular N-H⋯H-B interactions between the NH group originating from the primary amine and the BH group of the carborane cage. These interactions are rather strong (3.7 kcal/mol) and are likely to persist in solution. The reactions of 10-MeC≡N-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub> with secondary acyclic (Me<sub>2</sub>NH, Et<sub>2</sub>NH) and cyclic (piperidine, morpholine) amines result in amidines 10-R<sub>2</sub>NC(Me)=HN-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub> (R = Me, Et; R<sub>2</sub> = N(CH<sub>2</sub>)<sub>5</sub>, N(CH<sub>2</sub>CH<sub>2</sub>)<sub>2</sub>O) as single isomers, which, according to single crystal X-ray diffraction data, have the <i>E</i>-configuration. |
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| institution | DOAJ |
| issn | 1420-3049 |
| language | English |
| publishDate | 2025-02-01 |
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| spelling | doaj-art-7a887ce5c13b4ecbb144f9a36dbc6c912025-08-20T03:12:09ZengMDPI AGMolecules1420-30492025-02-0130482810.3390/molecules30040828Nucleophilic Addition Reactions to 10-Acetonitrilium Derivative of <i>nido</i>-Carborane and Intramolecular NH⋯HB Interactions in <i>N</i>-Alkyl Amidines 10-RNHC(Me)=NH-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub>Kirill R. Pakholkov0Ekaterina V. Bogdanova1Marina Yu. Stogniy2Kyrill Yu. Suponitsky3Sergey A. Anufriev4Igor B. Sivaev5Vladimir I. Bregadze6A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilov Str., 119991 Moscow, RussiaA.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilov Str., 119991 Moscow, RussiaA.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilov Str., 119991 Moscow, RussiaA.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilov Str., 119991 Moscow, RussiaA.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilov Str., 119991 Moscow, RussiaA.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilov Str., 119991 Moscow, RussiaA.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilov Str., 119991 Moscow, RussiaThe addition reactions of water, alcohols, and primary and secondary amines to the 10-acetonitrilium derivative of <i>nido</i>-carborane were studied. Hydrolysis of 10-MeC≡N-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub> results in iminol 10-MeC(OH)=HN-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub>, which, on treatment with a base, gives amide [10-MeC(=O)HN-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub>]<sup>−</sup>. The reactions of 10-MeC≡N-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub> with alcohols lead to imidates 10-ROC(Me)=HN-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub> (R = Me, Et) as mixtures of <i>E</i>- and <i>Z</i>-isomers. In the solid state, 10-MeOC(Me)=HN-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub> adopts <i>E</i>-configuration. The reactions of 10-MeC≡N-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub> with primary amines result in amidines 10-RNHC(Me)=HN-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub> (R = Me, Et) as mixtures of <i>E</i>- and <i>Z</i>-isomers. In the solid state 10-EtNHC(Me)=HN-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub> was found to have the <i>Z</i>-configuration, which is stabilized by intramolecular N-H⋯H-B interactions between the NH group originating from the primary amine and the BH group of the carborane cage. These interactions are rather strong (3.7 kcal/mol) and are likely to persist in solution. The reactions of 10-MeC≡N-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub> with secondary acyclic (Me<sub>2</sub>NH, Et<sub>2</sub>NH) and cyclic (piperidine, morpholine) amines result in amidines 10-R<sub>2</sub>NC(Me)=HN-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub> (R = Me, Et; R<sub>2</sub> = N(CH<sub>2</sub>)<sub>5</sub>, N(CH<sub>2</sub>CH<sub>2</sub>)<sub>2</sub>O) as single isomers, which, according to single crystal X-ray diffraction data, have the <i>E</i>-configuration.https://www.mdpi.com/1420-3049/30/4/828<i>nido</i>-carboraneacetonitrilium derivativeamideiminolimidatesamidines |
| spellingShingle | Kirill R. Pakholkov Ekaterina V. Bogdanova Marina Yu. Stogniy Kyrill Yu. Suponitsky Sergey A. Anufriev Igor B. Sivaev Vladimir I. Bregadze Nucleophilic Addition Reactions to 10-Acetonitrilium Derivative of <i>nido</i>-Carborane and Intramolecular NH⋯HB Interactions in <i>N</i>-Alkyl Amidines 10-RNHC(Me)=NH-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub> Molecules <i>nido</i>-carborane acetonitrilium derivative amide iminol imidates amidines |
| title | Nucleophilic Addition Reactions to 10-Acetonitrilium Derivative of <i>nido</i>-Carborane and Intramolecular NH⋯HB Interactions in <i>N</i>-Alkyl Amidines 10-RNHC(Me)=NH-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub> |
| title_full | Nucleophilic Addition Reactions to 10-Acetonitrilium Derivative of <i>nido</i>-Carborane and Intramolecular NH⋯HB Interactions in <i>N</i>-Alkyl Amidines 10-RNHC(Me)=NH-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub> |
| title_fullStr | Nucleophilic Addition Reactions to 10-Acetonitrilium Derivative of <i>nido</i>-Carborane and Intramolecular NH⋯HB Interactions in <i>N</i>-Alkyl Amidines 10-RNHC(Me)=NH-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub> |
| title_full_unstemmed | Nucleophilic Addition Reactions to 10-Acetonitrilium Derivative of <i>nido</i>-Carborane and Intramolecular NH⋯HB Interactions in <i>N</i>-Alkyl Amidines 10-RNHC(Me)=NH-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub> |
| title_short | Nucleophilic Addition Reactions to 10-Acetonitrilium Derivative of <i>nido</i>-Carborane and Intramolecular NH⋯HB Interactions in <i>N</i>-Alkyl Amidines 10-RNHC(Me)=NH-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub> |
| title_sort | nucleophilic addition reactions to 10 acetonitrilium derivative of i nido i carborane and intramolecular nh⋯hb interactions in i n i alkyl amidines 10 rnhc me nh 7 8 c sub 2 sub b sub 9 sub h sub 11 sub |
| topic | <i>nido</i>-carborane acetonitrilium derivative amide iminol imidates amidines |
| url | https://www.mdpi.com/1420-3049/30/4/828 |
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