| Summary: | The preparation of novel nitrilium derivatives of <i>closo</i>-dodecaborate anion [B<sub>12</sub>H<sub>11</sub>NCR]<sup>−</sup>, R = <i>n</i>-C<sub>3</sub>H<sub>7</sub>, <i>i</i>-C<sub>3</sub>H<sub>7</sub>, 4-C<sub>6</sub>H<sub>4</sub>CH<sub>3</sub>, 1-C<sub>10</sub>H<sub>7</sub> is described. Target compounds were obtained in good yields (up to 73%). The synthesis of target borylated nitrilium derivatives was characterised by the simplicity of the chemical apparatus and the absence of the necessity for the purification of desired compounds. The crystal structures of previously obtained [B<sub>12</sub>H<sub>11</sub>NCCH<sub>3</sub>]<sup>−</sup> and novel [B<sub>12</sub>H<sub>11</sub>NCC<sub>3</sub>H<sub>7</sub>]<sup>−</sup> were established with the help of X-ray structure analysis. DFT-analysis of several nitrilium derivatives [B<sub>12</sub>H<sub>11</sub>NCR]<sup>−</sup>, R = CH<sub>3</sub>, C<sub>3</sub>H<sub>7</sub>, 4-CH<sub>3</sub>C<sub>6</sub>H<sub>4</sub> was carried out. The main peculiarities of the C≡N bond of the <i>exo</i>-polyhedral substituent were revealed in terms of bond lengths, bond orders and atomic charges. The LUMO orbitals of the systems considered were examined for understanding of the electrophilic nature of the nitrilium derivatives of the <i>closo</i>-dodecaborate anion.
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