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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2024-11-01
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| author | Han-Ying Liu Kyle G. Pearce Michael S. Hill Mary F. Mahon |
| author_facet | Han-Ying Liu Kyle G. Pearce Michael S. Hill Mary F. Mahon |
| author_sort | Han-Ying Liu |
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| description | 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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| language | English |
| publishDate | 2024-11-01 |
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| spelling | doaj-art-bc2e4089a988467ba619dcd415b5a3332025-08-20T02:53:37ZengMDPI AGInorganics2304-67402024-11-01121230910.3390/inorganics12120309Oxidative Addition to Group 1 (K, Rb, Cs) Alumanyl Anions as a Route to <i>o</i>-Carboranyl (hydrido)aluminatesHan-Ying Liu0Kyle G. Pearce1Michael S. Hill2Mary F. Mahon3Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UKDepartment of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UKDepartment of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UKDepartment of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UKThe 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.https://www.mdpi.com/2304-6740/12/12/309bulky ligandaluminiumcarboranepotassiumrubidiumcaesium |
| spellingShingle | Han-Ying Liu Kyle G. Pearce Michael S. Hill Mary F. Mahon Oxidative Addition to Group 1 (K, Rb, Cs) Alumanyl Anions as a Route to <i>o</i>-Carboranyl (hydrido)aluminates Inorganics bulky ligand aluminium carborane potassium rubidium caesium |
| title | Oxidative Addition to Group 1 (K, Rb, Cs) Alumanyl Anions as a Route to <i>o</i>-Carboranyl (hydrido)aluminates |
| title_full | Oxidative Addition to Group 1 (K, Rb, Cs) Alumanyl Anions as a Route to <i>o</i>-Carboranyl (hydrido)aluminates |
| title_fullStr | Oxidative Addition to Group 1 (K, Rb, Cs) Alumanyl Anions as a Route to <i>o</i>-Carboranyl (hydrido)aluminates |
| title_full_unstemmed | Oxidative Addition to Group 1 (K, Rb, Cs) Alumanyl Anions as a Route to <i>o</i>-Carboranyl (hydrido)aluminates |
| title_short | Oxidative Addition to Group 1 (K, Rb, Cs) Alumanyl Anions as a Route to <i>o</i>-Carboranyl (hydrido)aluminates |
| title_sort | oxidative addition to group 1 k rb cs alumanyl anions as a route to i o i carboranyl hydrido aluminates |
| topic | bulky ligand aluminium carborane potassium rubidium caesium |
| url | https://www.mdpi.com/2304-6740/12/12/309 |
| work_keys_str_mv | AT hanyingliu oxidativeadditiontogroup1krbcsalumanylanionsasaroutetoioicarboranylhydridoaluminates AT kylegpearce oxidativeadditiontogroup1krbcsalumanylanionsasaroutetoioicarboranylhydridoaluminates AT michaelshill oxidativeadditiontogroup1krbcsalumanylanionsasaroutetoioicarboranylhydridoaluminates AT maryfmahon oxidativeadditiontogroup1krbcsalumanylanionsasaroutetoioicarboranylhydridoaluminates |