Monocarbaborane Anion Chemistry. Syntheses and Structures Within the closo Nine-Vertex System

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Title:Monocarbaborane Anion Chemistry. Syntheses and Structures Within the closo Nine-Vertex System
Creators:
Jelínek, Tomáš
Thornton-Pett, Mark
Kennedy, John D.
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 67, 7, pp. 1035-1050
Uncontrolled Keywords:Thermolyses, Iodination, Boranes, [4-CB<sub>8</sub>H<sub>9</sub>]<sup>-</sup>, Carboranes, Monocarbaboranes

Abstract

Reaction of HCHO with B<sub>10</sub>H<sub>14</sub> under aqueous alkaline conditions yields the <i>arachno</i> 10-vertex [6-CB<sub>9</sub>H<sub>14</sub>]<sup>-</sup> anion <strong>2</strong> (60%) which upon solid-state thermolysis as its Cs<sup>+</sup> salt yields the <i>closo</i> 9-vertex [4-CB<sub>8</sub>H<sub>9</sub>]<sup>-</sup> anion <strong>1</strong> (45%). MeCHO reacts similarly to give the <i>C</i>-methylated <i>arachno</i> [6-Me-6-CB<sub>9</sub>H<sub>13</sub>]<sup>-</sup> anion <strong>4</strong> (37%) which upon thermolysis gives the <i>closo</i> [4-Me-4-CB<sub>8</sub>H<sub>8</sub>]<sup>-</sup> anion <strong>3</strong> (72%). PhCHO with B<sub>10</sub>H<sub>14</sub> under alkaline conditions gives the <i>nido</i> 10-vertex [6-Ph-6-CB<sub>9</sub>H<sub>11</sub>]<sup>-</sup> anion <strong>6</strong> (85%) which upon thermolysis of its [NEt<sub>4</sub>]<sup>+</sup> salt gives the <i>closo</i> [4-Ph-4-CB<sub>8</sub>H<sub>8</sub>]<sup>-</sup> anion <strong>5</strong> (73%). In a preliminary iodination investigation, unsubstituted <i>closo</i> anion <strong>1</strong> with elemental I<sub>2</sub> in CH<sub>2</sub>Cl<sub>2</sub> gives approximately equimolar <i>closo</i> [4-CB<sub>8</sub>H<sub>8</sub>-3-I]<sup>-</sup> <strong>12</strong> and <i>closo</i> [4-CB<sub>8</sub>H<sub>8</sub>-5-I]<sup>-</sup> <strong>13</strong> (<i>ca</i> 60%) and smaller amounts of <i>closo</i> [4-CB<sub>8</sub>H<sub>7</sub>-5,6-I<sub>2</sub>]<sup>-</sup> <strong>14</strong> (12%). The [NEt<sub>4</sub>]<sup>+</sup> salts of <strong>1</strong>, <strong>3</strong> and <strong>5</strong> are characterised crystallographically, as is the [PMePh<sub>3</sub>]<sup>+</sup> salt of <strong>12</strong>. <p>

Title:Monocarbaborane Anion Chemistry. Syntheses and Structures Within the closo Nine-Vertex System
Creators:
Jelínek, Tomáš
Thornton-Pett, Mark
Kennedy, John D.
Uncontrolled Keywords:Thermolyses, Iodination, Boranes, [4-CB<sub>8</sub>H<sub>9</sub>]<sup>-</sup>, Carboranes, Monocarbaboranes
Divisions:Life and Chemical Sciences > Institute of Organic Chemistry and Biochemistry > Collection of Czechoslovak Chemical Communications
Journal or Publication Title:Collection of Czechoslovak Chemical Communications
Volume:67
Number:7
Page Range:pp. 1035-1050
ISSN:0010-0765
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc20021035UNSPECIFIED
ID Code:1971
Item Type:Article
Deposited On:06 Feb 2009 17:14
Last Modified:06 Feb 2009 16:14

Citation

Jelínek, Tomáš; Thornton-Pett, Mark; Kennedy, John D. (2002) Monocarbaborane Anion Chemistry. Syntheses and Structures Within the closo Nine-Vertex System. Collection of Czechoslovak Chemical Communications, 67 (7). pp. 1035-1050. ISSN 0010-0765

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