Dimethyloxonium and Methoxy Derivatives of nido-Carborane and Metal Complexes Thereof

9-Dimethyloxonium, 10-dimethyloxonium, 9-methoxy and 10-methoxy derivatives of nido-carborane (9-Me2O-7,8-C2B9H11, 10-Me2O-7,8-C2B9&...

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Main Authors:	Marina Yu. Stogniy, Svetlana A. Erokhina, Irina D. Kosenko, Andrey A. Semioshkin, Igor B. Sivaev
Format:	Article
Language:	English
Published:	MDPI AG 2019-03-01
Series:	Inorganics
Subjects:	<i>nido</i>-carborane iron bis(dicarbollide) cobalt bis(dicarbollide) dimethyloxonium derivatives methoxy derivatives synthesis properties
Online Access:	https://www.mdpi.com/2304-6740/7/4/46

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spelling	doaj-7337b9895711443bbce29546832a02e22020-11-25T00:55:53ZengMDPI AGInorganics2304-67402019-03-01744610.3390/inorganics7040046inorganics7040046Dimethyloxonium and Methoxy Derivatives of <i>nido</i>-Carborane and Metal Complexes ThereofMarina Yu. Stogniy0Svetlana A. Erokhina1Irina D. Kosenko2Andrey A. Semioshkin3Igor B. Sivaev4A.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, Russia9-Dimethyloxonium, 10-dimethyloxonium, 9-methoxy and 10-methoxy derivatives of <i>nido</i>-carborane (9-Me<sub>2</sub>O-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub>, 10-Me<sub>2</sub>O-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub>, [9-MeO-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub>]<sup>−</sup>, and [10-MeO-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub>]<sup>−</sup>, respectively) were prepared by the reaction of the parent <i>nido</i>-carborane [7,8-C<sub>2</sub>B<sub>9</sub>H<sub>12</sub>]<sup>−</sup> with mercury(II) chloride in a mixture of benzene and dimethoxymethane. Reactions of the 9 and 10-dimethyloxonium derivatives with triethylamine, pyridine, and 3-methyl-6-nitro-1<i>H</i>-indazole result in their N-methylation with the formation of the corresponding salts with 9 and 10-methoxy-<i>nido</i>-carborane anions. The reaction of the symmetrical methoxy derivative [10-MeO-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub>]<sup>−</sup> with anhydrous FeCl<sub>2</sub> in tetrahydrofuran in the presence of <i>t</i>-BuOK results in the corresponding paramagnetic iron bis(dicarbollide) complex [8,8′-(MeO)<sub>2</sub>-3,3′-Fe(1,2-C<sub>2</sub>B<sub>9</sub>H<sub>10</sub>)<sub>2</sub>]<sup>−</sup>, whereas the similar reactions of the asymmetrical methoxy derivative [9-MeO-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub>]<sup>−</sup> with FeCl<sub>2</sub> and CoCl<sub>2</sub> presumably produce the 4,7′-isomers [4,7′-(MeO)<sub>2</sub>-3,3′-M(1,2-C<sub>2</sub>B<sub>9</sub>H<sub>10</sub>)<sub>2</sub>]<sup>−</sup> (M = Fe, Co) rather than a mixture of <i>rac</i>-4,7′- and <i>meso</i>-4,4′-isomers.https://www.mdpi.com/2304-6740/7/4/46<i>nido</i>-carboraneiron bis(dicarbollide)cobalt bis(dicarbollide)dimethyloxonium derivativesmethoxy derivativessynthesisproperties
collection	DOAJ
language	English
format	Article
sources	DOAJ
author	Marina Yu. Stogniy Svetlana A. Erokhina Irina D. Kosenko Andrey A. Semioshkin Igor B. Sivaev
spellingShingle	Marina Yu. Stogniy Svetlana A. Erokhina Irina D. Kosenko Andrey A. Semioshkin Igor B. Sivaev Dimethyloxonium and Methoxy Derivatives of <i>nido</i>-Carborane and Metal Complexes Thereof Inorganics <i>nido</i>-carborane iron bis(dicarbollide) cobalt bis(dicarbollide) dimethyloxonium derivatives methoxy derivatives synthesis properties
author_facet	Marina Yu. Stogniy Svetlana A. Erokhina Irina D. Kosenko Andrey A. Semioshkin Igor B. Sivaev
author_sort	Marina Yu. Stogniy
title	Dimethyloxonium and Methoxy Derivatives of <i>nido</i>-Carborane and Metal Complexes Thereof
title_short	Dimethyloxonium and Methoxy Derivatives of <i>nido</i>-Carborane and Metal Complexes Thereof
title_full	Dimethyloxonium and Methoxy Derivatives of <i>nido</i>-Carborane and Metal Complexes Thereof
title_fullStr	Dimethyloxonium and Methoxy Derivatives of <i>nido</i>-Carborane and Metal Complexes Thereof
title_full_unstemmed	Dimethyloxonium and Methoxy Derivatives of <i>nido</i>-Carborane and Metal Complexes Thereof
title_sort	dimethyloxonium and methoxy derivatives of <i>nido</i>-carborane and metal complexes thereof
publisher	MDPI AG
series	Inorganics
issn	2304-6740
publishDate	2019-03-01
description	9-Dimethyloxonium, 10-dimethyloxonium, 9-methoxy and 10-methoxy derivatives of <i>nido</i>-carborane (9-Me<sub>2</sub>O-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub>, 10-Me<sub>2</sub>O-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub>, [9-MeO-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub>]<sup>−</sup>, and [10-MeO-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub>]<sup>−</sup>, respectively) were prepared by the reaction of the parent <i>nido</i>-carborane [7,8-C<sub>2</sub>B<sub>9</sub>H<sub>12</sub>]<sup>−</sup> with mercury(II) chloride in a mixture of benzene and dimethoxymethane. Reactions of the 9 and 10-dimethyloxonium derivatives with triethylamine, pyridine, and 3-methyl-6-nitro-1<i>H</i>-indazole result in their N-methylation with the formation of the corresponding salts with 9 and 10-methoxy-<i>nido</i>-carborane anions. The reaction of the symmetrical methoxy derivative [10-MeO-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub>]<sup>−</sup> with anhydrous FeCl<sub>2</sub> in tetrahydrofuran in the presence of <i>t</i>-BuOK results in the corresponding paramagnetic iron bis(dicarbollide) complex [8,8′-(MeO)<sub>2</sub>-3,3′-Fe(1,2-C<sub>2</sub>B<sub>9</sub>H<sub>10</sub>)<sub>2</sub>]<sup>−</sup>, whereas the similar reactions of the asymmetrical methoxy derivative [9-MeO-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub>]<sup>−</sup> with FeCl<sub>2</sub> and CoCl<sub>2</sub> presumably produce the 4,7′-isomers [4,7′-(MeO)<sub>2</sub>-3,3′-M(1,2-C<sub>2</sub>B<sub>9</sub>H<sub>10</sub>)<sub>2</sub>]<sup>−</sup> (M = Fe, Co) rather than a mixture of <i>rac</i>-4,7′- and <i>meso</i>-4,4′-isomers.
topic	<i>nido</i>-carborane iron bis(dicarbollide) cobalt bis(dicarbollide) dimethyloxonium derivatives methoxy derivatives synthesis properties
url	https://www.mdpi.com/2304-6740/7/4/46
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Dimethyloxonium and Methoxy Derivatives of <i>nido</i>-Carborane and Metal Complexes Thereof

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