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<p>Reactions of cesium salts of substituted <i>nido</i>-carborane anions [<i>nido</i>-5-Ph-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub>]<sup>-</sup> (<b>1</b>) and [<i>nido</i>-5,6-Ph<sub>2</sub>-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>10</sub>]<sup>-</sup> (<b>2</b>) bearing bulky phenyl groups at boron atoms in the lower bent of carborane ligand with RuCl<sub>2</sub>(PPh<sub>3</sub>)dppb (<b>3</b>) in benzene solution led to the novel 18-e <i>closo</i>-ruthenacarboranes 3,3-(Ph<sub>2</sub>P(CH<sub>2</sub>)<sub>4</sub>PPh<sub>2</sub>)-3-H-3-Cl-9-Ph-12-X-<i>closo</i>-3,1,2-RuC<sub>2</sub>B<sub>9</sub>H<sub>9</sub> (X = H (<b>4</b>), Ph (<b>5</b>)). Reactions of the obtained complexes with carbon tetrachloride allowed to obtain corresponding 17-e Ru(III) complexes 3,3-(Ph<sub>2</sub>P(CH<sub>2</sub>)<sub>4</sub>PPh<sub>2</sub>)-3-Cl-9-Ph-12-X-<i>closo</i>-3,1,2-RuC<sub>2</sub>B<sub>9</sub>H<sub>10</sub> (X = H (<b>7</b>), Ph (<b>8</b>)). The reaction of <b>4</b> with isopropylamine in acetonitrile leads to the formation of the corresponding acetonitrile complex 3,3-(Ph<sub>2</sub>P(CH<sub>2</sub>)<sub>4</sub>PPh<sub>2</sub>)-3-CH<sub>3</sub>CN-9-Ph-12-<i>closo</i>-3,1,2-RuC<sub>2</sub>B<sub>9</sub>H<sub>10</sub> (<b>10</b>). The novel ruthenacarborane clusters <b>5</b> and <b>8</b> were characterized by single crystal X-ray diffraction which unambiguously confirmed the proposed structures. The cyclic voltammetry studies of compounds <b>4</b> and <b>5</b> showed its ability to reversible reduction to the corresponding Ru(II) species.</p>

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Ruthenacarboranes Based on 5-Phenyl- and 5,6-Diphenyl Dicarbollide Ligands. Synthesis and Transformations

  • 期刊论文

  • 发表日期：

    2025年7月18日

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  • Ivan D. Grishin,
  • Anastasiya M. Zimina,
  • Viktoriya N. Kirpichnikova,
  • Sergey A. Anufriev,
  • Nikolay V. Somov,
  • Ilya I. Vorobyov,
  • Igor B. Sivaev

摘要

Reactions of cesium salts of substituted nido-carborane anions [nido-5-Ph-7,8-C2B9H11]- (1) and [nido-5,6-Ph2-7,8-C2B9H10]- (2) bearing bulky phenyl groups at boron atoms in the lower bent of carborane ligand with RuCl2(PPh3)dppb (3) in benzene solution led to the novel 18-e closo-ruthenacarboranes 3,3-(Ph2P(CH2)4PPh2)-3-H-3-Cl-9-Ph-12-X-closo-3,1,2-RuC2B9H9 (X = H (4), Ph (5)). Reactions of the obtained complexes with carbon tetrachloride allowed to obtain corresponding 17-e Ru(III) complexes 3,3-(Ph2P(CH2)4PPh2)-3-Cl-9-Ph-12-X-closo-3,1,2-RuC2B9H10 (X = H (7), Ph (8)). The reaction of 4 with isopropylamine in acetonitrile leads to the formation of the corresponding acetonitrile complex 3,3-(Ph2P(CH2)4PPh2)-3-CH3CN-9-Ph-12-closo-3,1,2-RuC2B9H10 (10). The novel ruthenacarborane clusters 5 and 8 were characterized by single crystal X-ray diffraction which unambiguously confirmed the proposed structures. The cyclic voltammetry studies of compounds 4 and 5 showed its ability to reversible reduction to the corresponding Ru(II) species.