Oxidative Addition to Group 1 (K, Rb, Cs) Alumanyl Anions as a Route to o-Carboranyl(hydrido)aluminates

Michael Hill; Han-Ying Liu; Kyle Pearce; Mary Mahon

doi:10.3390/inorganics12120309

Oxidative Addition to Group 1 (K, Rb, Cs) Alumanyl Anions as a Route to o-Carboranyl(hydrido)aluminates

Michael Hill, Han-Ying Liu, Kyle Pearce, Mary Mahon

Research output: Contribution to journal › Article › peer-review

Abstract

The kinetic stability provided by the sterically demanding {SiNDipp}2 dianion (SiNDipp = {CH2SiMe2NDipp}2; Dipp = 2,6-i-Pr2C6H3) is intrinsic to the isolation of not only the group 1 alumanyl reagents ([{SiNDipp}AlM]2; M = K, Rb, Cs) but also facilitates the completely selective oxidative addition of a C-H bond of 1,2-C2B10H12 to the aluminium centre. In each case, the resultant compounds comprise a 4-coordinate o-carboranyl(hydrido)aluminate anion, [(SiNDipp)Al(H)(1,2-C2B10H11)], in which the carboranyl cage is bonded to aluminium by an Al-C sigma 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+ ionic radius as group 1 is descended. Whereas 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 2-dimensional assembly of hexameric aggregates.

Original language	English
Article number	309
Journal	Inorganics
Volume	12
Issue number	12
Early online date	27 Nov 2024
DOIs	https://doi.org/10.3390/inorganics12120309
Publication status	Published - 27 Nov 2024

Data Availability Statement

NMR spectra [51] and crystal data [52,53,54] are given in the Supporting Information. Crystal data and details of the data collection and refinement are given in Table S1. Crystallographic data for 1, 2, and 3, respectively, have been deposited with the Cambridge Crystallographic Data Centre (CCDC 2369273, 2369274, 2393518). Copies of this information may be obtained free of charge from The Director, CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK (fax: +44-1223-336033; email: [email protected] or http://www.ccdc.cam.ac.uk)

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10.3390/inorganics12120309Licence: CC BY

Alkaline Element Z-type Ligands for Tunable Base Metal Catalysis
Hill, M. (PI) & Liu, H.-Y. (Researcher)
The Leverhulme Trust
1/09/23 → 31/08/26
Project: UK charity

Cite this

@article{656d68256f644062896fd5b244ef72a7,

title = "Oxidative Addition to Group 1 (K, Rb, Cs) Alumanyl Anions as a Route to o-Carboranyl(hydrido)aluminates",

abstract = "The kinetic stability provided by the sterically demanding {SiNDipp}2 dianion (SiNDipp = {CH2SiMe2NDipp}2; Dipp = 2,6-i-Pr2C6H3) is intrinsic to the isolation of not only the group 1 alumanyl reagents ([{SiNDipp}AlM]2; M = K, Rb, Cs) but also facilitates the completely selective oxidative addition of a C-H bond of 1,2-C2B10H12 to the aluminium centre. In each case, the resultant compounds comprise a 4-coordinate o-carboranyl(hydrido)aluminate anion, [(SiNDipp)Al(H)(1,2-C2B10H11)], in which the carboranyl cage is bonded to aluminium by an Al-C sigma 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+ ionic radius as group 1 is descended. Whereas 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 2-dimensional assembly of hexameric aggregates.",

author = "Michael Hill and Han-Ying Liu and Kyle Pearce and Mary Mahon",

year = "2024",

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day = "27",

doi = "10.3390/inorganics12120309",

language = "English",

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TY - JOUR

T1 - Oxidative Addition to Group 1 (K, Rb, Cs) Alumanyl Anions as a Route to o-Carboranyl(hydrido)aluminates

AU - Hill, Michael

AU - Liu, Han-Ying

AU - Pearce, Kyle

AU - Mahon, Mary

PY - 2024/11/27

Y1 - 2024/11/27

N2 - The kinetic stability provided by the sterically demanding {SiNDipp}2 dianion (SiNDipp = {CH2SiMe2NDipp}2; Dipp = 2,6-i-Pr2C6H3) is intrinsic to the isolation of not only the group 1 alumanyl reagents ([{SiNDipp}AlM]2; M = K, Rb, Cs) but also facilitates the completely selective oxidative addition of a C-H bond of 1,2-C2B10H12 to the aluminium centre. In each case, the resultant compounds comprise a 4-coordinate o-carboranyl(hydrido)aluminate anion, [(SiNDipp)Al(H)(1,2-C2B10H11)], in which the carboranyl cage is bonded to aluminium by an Al-C sigma 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+ ionic radius as group 1 is descended. Whereas 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 2-dimensional assembly of hexameric aggregates.

AB - The kinetic stability provided by the sterically demanding {SiNDipp}2 dianion (SiNDipp = {CH2SiMe2NDipp}2; Dipp = 2,6-i-Pr2C6H3) is intrinsic to the isolation of not only the group 1 alumanyl reagents ([{SiNDipp}AlM]2; M = K, Rb, Cs) but also facilitates the completely selective oxidative addition of a C-H bond of 1,2-C2B10H12 to the aluminium centre. In each case, the resultant compounds comprise a 4-coordinate o-carboranyl(hydrido)aluminate anion, [(SiNDipp)Al(H)(1,2-C2B10H11)], in which the carboranyl cage is bonded to aluminium by an Al-C sigma 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+ ionic radius as group 1 is descended. Whereas 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 2-dimensional assembly of hexameric aggregates.

U2 - 10.3390/inorganics12120309

DO - 10.3390/inorganics12120309

M3 - Article

SN - 2304-6740

VL - 12

JO - Inorganics

JF - Inorganics

IS - 12

M1 - 309

ER -

Oxidative Addition to Group 1 (K, Rb, Cs) Alumanyl Anions as a Route to o-Carboranyl(hydrido)aluminates

Abstract

Data Availability Statement

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Alkaline Element Z-type Ligands for Tunable Base Metal Catalysis

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