Oxidative Addition to Group 1 (K, Rb, Cs) Alumanyl Anions as a Route to <i>o</i>-Carboranyl (hydrido)aluminates
The kinetic stability provided by the sterically demanding {SiN<sup>Dipp</sup>}<sup>2−</sup> dianion (SiN<sup>Dipp</sup> = {CH<sub>2</sub>SiMe<sub>2</sub>NDipp}<sub>2</sub>; Dipp = 2,6-<i>i</i>-Pr<sub>2</sub...
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| Main Authors: | , , , |
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| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2024-11-01
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| Series: | Inorganics |
| Subjects: | |
| Online Access: | https://www.mdpi.com/2304-6740/12/12/309 |
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| Summary: | The kinetic stability provided by the sterically demanding {SiN<sup>Dipp</sup>}<sup>2−</sup> dianion (SiN<sup>Dipp</sup> = {CH<sub>2</sub>SiMe<sub>2</sub>NDipp}<sub>2</sub>; Dipp = 2,6-<i>i</i>-Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>) is intrinsic to the isolation of not only the group 1 alumanyl reagents ([{SiN<sup>Dipp</sup>}AlM]<sub>2</sub>; M = K, Rb, Cs) but also facilitates the completely selective oxidative addition of a C-H bond of 1,2-C<sub>2</sub>B<sub>10</sub>H<sub>12</sub> to the aluminium centre. In each case, the resultant compounds comprise a four-coordinate <i>o</i>-carboranyl (hydrido)aluminate anion, [(SiN<sup>Dipp</sup>)Al(H)(1,2-C<sub>2</sub>B<sub>10</sub>H<sub>11</sub>)]<sup>−</sup>, in which the carboranyl cage is bonded to aluminium by an Al-C σ bond. Although the anions further assemble as extended network structures based on Al-H∙∙∙M, B-H∙∙∙M, and C-H∙∙∙M interactions, each structure is unique due to the significant variation in M<sup>+</sup> ionic radius as group 1 is descended. The potassium derivative crystallises as a one-dimensional polymer, its rubidium analogue is a dimer due to the polyhapto-sequestration of a molecule of benzene solvent within the alkali metal coordination sphere, and the caesium species is a two-dimensional assembly of hexameric aggregates. |
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| ISSN: | 2304-6740 |