Synthesis and Catalytic Properties of Novel Ruthenacarboranes Based on nido-[5-Me-7,8-C2B9H10]2− and nido-[5,6-Me2-7,8-C2B9H9]2− Dicarbollide Ligands

The effect of methyl substituents in the lower belt of dicarbollide ligands on the redox potential of ruthenacarboranes based thereof, as well as the ability of the metallacarboranes obtained to catalyze radical polymerization with atom transfer were studied. For this purpose, a new approach to the...

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Autores principales:	Ivan D. Grishin, Anastasiya M. Zimina, Sergey A. Anufriev, Nadezhda A. Knyazeva, Alexander V. Piskunov, Fedor M. Dolgushin, Igor B. Sivaev
Formato:	article
Lenguaje:	EN
Publicado:	MDPI AG 2021
Materias:	ruthenacarborane synthesis X-ray structure electrochemistry ATRP catalysis Chemical technology TP1-1185 Chemistry QD1-999
Acceso en línea:	https://doaj.org/article/e5f07f312214410187db28da34f8edbe
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spelling	oai:doaj.org-article:e5f07f312214410187db28da34f8edbe2021-11-25T17:06:57ZSynthesis and Catalytic Properties of Novel Ruthenacarboranes Based on <i>nido</i>-[5-Me-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>10</sub>]<sup>2−</sup> and <i>nido</i>-[5,6-Me<sub>2</sub>-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>9</sub>]<sup>2−</sup> Dicarbollide Ligands10.3390/catal111114092073-4344https://doaj.org/article/e5f07f312214410187db28da34f8edbe2021-11-01T00:00:00Zhttps://www.mdpi.com/2073-4344/11/11/1409https://doaj.org/toc/2073-4344The effect of methyl substituents in the lower belt of dicarbollide ligands on the redox potential of ruthenacarboranes based thereof, as well as the ability of the metallacarboranes obtained to catalyze radical polymerization with atom transfer were studied. For this purpose, a new approach to the synthesis of <i>closo</i>-ruthenacarboranes based on substituted dicarbollide ligands was developed and six new complexes 3,3-(Ph<sub>2</sub>P(CH<sub>2</sub>)<sub>4</sub>PPh<sub>2</sub>)-3-H-3-Cl-9-Me-12-X-<i>closo</i>-3,1,2-RuC<sub>2</sub>B<sub>9</sub>H<sub>9</sub>, 3,3,8-(Ph<sub>2</sub>P(CH<sub>2</sub>)<sub>4</sub>PPh-μ-(C<sub>6</sub>H<sub>4</sub>-<i>o</i>))-3-Cl-9-Me-12-X-<i>closo</i>-3,1,2-RuC<sub>2</sub>B<sub>9</sub>H<sub>8</sub> and 3,3,4,8-(Ph<sub>2</sub>P(CH<sub>2</sub>)<sub>4</sub>P-μ-(C<sub>6</sub>H<sub>4</sub>-<i>o</i>)<sub>2</sub>)-3-Cl-9-Me-9-X-<i>closo</i>-3,1,2-RuC<sub>2</sub>B<sub>9</sub>H<sub>7</sub> (X = H, Me) were synthetized and characterized by single crystal X-ray diffraction, NMR and ESR spectroscopy and MALDI TOF mass-spectrometry. Comparison of the values of the redox potentials of the synthesized ruthenium complexes in 1,2-dichloroethane with the values previously found for the corresponding ruthenacarboranes based on the parent dicarbollide anion showed that the introduction of methyl substituents into the carborane cage led to a decrease in the redox potentials of the complexes, which made them more preferable catalysts for ATRP. Test experiments on the polymerization of MMA showed that the synthesized ruthenacarboranes were effective catalysts for ATRP, the most active being the complex with two methyl groups and two <i>ortho</i>-phenylenecycloboronated fragments.Ivan D. GrishinAnastasiya M. ZiminaSergey A. AnufrievNadezhda A. KnyazevaAlexander V. PiskunovFedor M. DolgushinIgor B. SivaevMDPI AGarticleruthenacarboranesynthesisX-ray structureelectrochemistryATRP catalysisChemical technologyTP1-1185ChemistryQD1-999ENCatalysts, Vol 11, Iss 1409, p 1409 (2021)
institution	DOAJ
collection	DOAJ
language	EN
topic	ruthenacarborane synthesis X-ray structure electrochemistry ATRP catalysis Chemical technology TP1-1185 Chemistry QD1-999
spellingShingle	ruthenacarborane synthesis X-ray structure electrochemistry ATRP catalysis Chemical technology TP1-1185 Chemistry QD1-999 Ivan D. Grishin Anastasiya M. Zimina Sergey A. Anufriev Nadezhda A. Knyazeva Alexander V. Piskunov Fedor M. Dolgushin Igor B. Sivaev Synthesis and Catalytic Properties of Novel Ruthenacarboranes Based on <i>nido</i>-[5-Me-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>10</sub>]<sup>2−</sup> and <i>nido</i>-[5,6-Me<sub>2</sub>-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>9</sub>]<sup>2−</sup> Dicarbollide Ligands
description	The effect of methyl substituents in the lower belt of dicarbollide ligands on the redox potential of ruthenacarboranes based thereof, as well as the ability of the metallacarboranes obtained to catalyze radical polymerization with atom transfer were studied. For this purpose, a new approach to the synthesis of <i>closo</i>-ruthenacarboranes based on substituted dicarbollide ligands was developed and six new complexes 3,3-(Ph<sub>2</sub>P(CH<sub>2</sub>)<sub>4</sub>PPh<sub>2</sub>)-3-H-3-Cl-9-Me-12-X-<i>closo</i>-3,1,2-RuC<sub>2</sub>B<sub>9</sub>H<sub>9</sub>, 3,3,8-(Ph<sub>2</sub>P(CH<sub>2</sub>)<sub>4</sub>PPh-μ-(C<sub>6</sub>H<sub>4</sub>-<i>o</i>))-3-Cl-9-Me-12-X-<i>closo</i>-3,1,2-RuC<sub>2</sub>B<sub>9</sub>H<sub>8</sub> and 3,3,4,8-(Ph<sub>2</sub>P(CH<sub>2</sub>)<sub>4</sub>P-μ-(C<sub>6</sub>H<sub>4</sub>-<i>o</i>)<sub>2</sub>)-3-Cl-9-Me-9-X-<i>closo</i>-3,1,2-RuC<sub>2</sub>B<sub>9</sub>H<sub>7</sub> (X = H, Me) were synthetized and characterized by single crystal X-ray diffraction, NMR and ESR spectroscopy and MALDI TOF mass-spectrometry. Comparison of the values of the redox potentials of the synthesized ruthenium complexes in 1,2-dichloroethane with the values previously found for the corresponding ruthenacarboranes based on the parent dicarbollide anion showed that the introduction of methyl substituents into the carborane cage led to a decrease in the redox potentials of the complexes, which made them more preferable catalysts for ATRP. Test experiments on the polymerization of MMA showed that the synthesized ruthenacarboranes were effective catalysts for ATRP, the most active being the complex with two methyl groups and two <i>ortho</i>-phenylenecycloboronated fragments.
format	article
author	Ivan D. Grishin Anastasiya M. Zimina Sergey A. Anufriev Nadezhda A. Knyazeva Alexander V. Piskunov Fedor M. Dolgushin Igor B. Sivaev
author_facet	Ivan D. Grishin Anastasiya M. Zimina Sergey A. Anufriev Nadezhda A. Knyazeva Alexander V. Piskunov Fedor M. Dolgushin Igor B. Sivaev
author_sort	Ivan D. Grishin
title	Synthesis and Catalytic Properties of Novel Ruthenacarboranes Based on <i>nido</i>-[5-Me-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>10</sub>]<sup>2−</sup> and <i>nido</i>-[5,6-Me<sub>2</sub>-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>9</sub>]<sup>2−</sup> Dicarbollide Ligands
title_short	Synthesis and Catalytic Properties of Novel Ruthenacarboranes Based on <i>nido</i>-[5-Me-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>10</sub>]<sup>2−</sup> and <i>nido</i>-[5,6-Me<sub>2</sub>-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>9</sub>]<sup>2−</sup> Dicarbollide Ligands
title_full	Synthesis and Catalytic Properties of Novel Ruthenacarboranes Based on <i>nido</i>-[5-Me-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>10</sub>]<sup>2−</sup> and <i>nido</i>-[5,6-Me<sub>2</sub>-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>9</sub>]<sup>2−</sup> Dicarbollide Ligands
title_fullStr	Synthesis and Catalytic Properties of Novel Ruthenacarboranes Based on <i>nido</i>-[5-Me-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>10</sub>]<sup>2−</sup> and <i>nido</i>-[5,6-Me<sub>2</sub>-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>9</sub>]<sup>2−</sup> Dicarbollide Ligands
title_full_unstemmed	Synthesis and Catalytic Properties of Novel Ruthenacarboranes Based on <i>nido</i>-[5-Me-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>10</sub>]<sup>2−</sup> and <i>nido</i>-[5,6-Me<sub>2</sub>-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>9</sub>]<sup>2−</sup> Dicarbollide Ligands
title_sort	synthesis and catalytic properties of novel ruthenacarboranes based on <i>nido</i>-[5-me-7,8-c<sub>2</sub>b<sub>9</sub>h<sub>10</sub>]<sup>2−</sup> and <i>nido</i>-[5,6-me<sub>2</sub>-7,8-c<sub>2</sub>b<sub>9</sub>h<sub>9</sub>]<sup>2−</sup> dicarbollide ligands
publisher	MDPI AG
publishDate	2021
url	https://doaj.org/article/e5f07f312214410187db28da34f8edbe
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Synthesis and Catalytic Properties of Novel Ruthenacarboranes Based on <i>nido</i>-[5-Me-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>10</sub>]<sup>2−</sup> and <i>nido</i>-[5,6-Me<sub>2</sub>-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>9</sub>]<sup>2−</sup> Dicarbollide Ligands

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