Synthesis and characterization of dicarboranylmethylammonium polyoxometallates

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Title:Synthesis and characterization of dicarboranylmethylammonium polyoxometallates
Creators:
Macías, Ramón
Kennedy, John D.
Bould, Jonathan
Thornton-Pett, Mark
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 75, 11, pp. 1075-1096
Uncontrolled Keywords:Crystal structures, Carboranes, Polyoxometallates, Hydrogen bonds, Hybrid salts

Abstract

The reaction of [C<sub>2</sub>B<sub>10</sub>H<sub>11</sub>CH<sub>2</sub>NH<sub>3</sub>]Cl (<b>3</b>) with [NH<sub>4</sub>]<sub>6</sub>[Mo<sub>7</sub>O<sub>24</sub>][H<sub>2</sub>O]<sub>4</sub> in water instantly afforded a white precipitate: crystallization from acetone–hexane thence gave the hybrid dicarborane octamolybdate salt, [C<sub>2</sub>B<sub>10</sub>H<sub>11</sub>CH<sub>2</sub>NH<sub>3</sub>]<sub>2</sub>[C<sub>2</sub>B<sub>10</sub>H<sub>11</sub>CH<sub>2</sub>NH=CMe<sub>2</sub>]<sub>2</sub>[Mo<sub>8</sub>O<sub>26</sub>][Me<sub>2</sub>CO]<sub>4.5</sub> (<b>5</b>), whereas crystallization from acetonitrile–ether gave three further salts: [C<sub>2</sub>B<sub>10</sub>H<sub>11</sub>CH<sub>2</sub>NH<sub>3</sub>]<sub>2</sub>[C<sub>2</sub>B<sub>10</sub>H<sub>11</sub>CH<sub>2</sub>NH<sub>2</sub>CHMe<sub>2</sub>]<sub>2</sub>[Mo<sub>8</sub>O<sub>26</sub>][MeCN]<sub>2</sub> (<b>6</b>), [C<sub>2</sub>B<sub>10</sub>H<sub>11</sub>CH<sub>2</sub>NH<sub>3</sub>]<sub>4</sub>[Mo<sub>8</sub>O<sub>26</sub>][MeCN]<sub>2</sub>[Et<sub>2</sub>O]<sub>2</sub> (<b>7</b>) and [C<sub>2</sub>B<sub>10</sub>H<sub>11</sub>CH<sub>2</sub>NH<sub>3</sub>]<sub>2</sub>[C<sub>2</sub>B<sub>10</sub>H<sub>11</sub>CH<sub>2</sub>NH<sub>2</sub>Et]<sub>2</sub>[Mo<sub>8</sub>O<sub>26</sub>][MeCN]<sub>2</sub> (<b>8</b>). Similarly, treatment of an acidified solution of Na<sub>2</sub>WO<sub>4</sub> with [C<sub>2</sub>B<sub>10</sub>H<sub>11</sub>CH<sub>2</sub>NH<sub>3</sub>]Cl (<b>3</b>) in water also yielded a white precipitate: crystallization from acetone–hexane afforded the salt [C<sub>2</sub>B<sub>10</sub>H<sub>11</sub>CH<sub>2</sub>NH=CHMe<sub>2</sub>]<sub>4</sub>[W<sub>10</sub>O<sub>32</sub>][H<sub>2</sub>O]<sub>2</sub>[Me<sub>2</sub>CO]<sub>4</sub> (<b>10</b>), whereas crystallization from acetonitrile–ether gave the double salt [C<sub>2</sub>B<sub>10</sub>H<sub>11</sub>CH<sub>2</sub>NH<sub>3</sub>]<sub>2</sub>[C<sub>5</sub>H<sub>5</sub>NH]<sub>2</sub>[W<sub>10</sub>O<sub>32</sub>][MeCN]<sub>2</sub>-[Et<sub>2</sub>O] (<b>11</b>). All these ‘globule–globule’ salts <b>5</b>, <b>6</b>, <b>8</b>, <b>10</b> and <b>11</b> have been characterized by single-crystal X-ray diffraction analyses. Crystal structures reveal the presence of various small solvate molecules, together with an extensive network of hydrogen bonds between ammonium groups and oxygen atoms of the isopolyoxometallates. The isopropyl substituent in one of the carborane cations of the salts <b>6</b> and the ethyl substituent in one of the carborane cations of salts <b>8</b> may result from occluded isopropanol and ethanol in the starting salt <b>3</b> with alkylations of the primary ammonium group being assisted by isopolymolybdate anions. The presence of the pyridinium cation in <b>11</b> is believed to arise from contamination during work-up the reaction mixture.

Title:Synthesis and characterization of dicarboranylmethylammonium polyoxometallates
Creators:
Macías, Ramón
Kennedy, John D.
Bould, Jonathan
Thornton-Pett, Mark
Uncontrolled Keywords:Crystal structures, Carboranes, Polyoxometallates, Hydrogen bonds, Hybrid salts
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:75
Number:11
Page Range:pp. 1075-1096
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc2010056UNSPECIFIED
ID Code:6264
Item Type:Article
Deposited On:12 Nov 2010 12:04
Last Modified:12 Nov 2010 11:04

Citation

Macías, Ramón; Kennedy, John D.; Bould, Jonathan; Thornton-Pett, Mark (2010) Synthesis and characterization of dicarboranylmethylammonium polyoxometallates. Collection of Czechoslovak Chemical Communications, 75 (11). pp. 1075-1096.

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