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

Michael Hill; Han-Ying Liu; Kyle G. 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 G. Pearce, Mary Mahon

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

1 Citation (SciVal)

Abstract

The kinetic stability provided by the sterically demanding {SiN ^Dipp} ²⁻ dianion (SiN ^Dipp = {CH ₂SiMe ₂NDipp} ₂; Dipp = 2,6-i-Pr ₂C ₆H ₃) is intrinsic to the isolation of not only the group 1 alumanyl reagents ([{SiN ^Dipp}AlM] ₂; M = K, Rb, Cs) but also facilitates the completely selective oxidative addition of a C-H bond of 1,2-C ₂B ₁₀H ₁₂ to the aluminium centre. In each case, the resultant compounds comprise a four-coordinate o-carboranyl (hydrido)aluminate anion, [(SiN ^Dipp)Al(H)(1,2-C ₂B ₁₀H ₁₁)] ⁻, 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 ⁺ 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.

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 - 31 Dec 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)

Funding

We thank the EPSRC (EP/X01181X/1) for their support in this work.

Funders	Funder number
Engineering and Physical Sciences Research Council	EP/X01181X/1
Engineering and Physical Sciences Research Council

Keywords

aluminium
bulky ligand
caesium
carborane
potassium
rubidium

ASJC Scopus subject areas

Inorganic Chemistry

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10.3390/inorganics12120309Licence: CC BY

Cite this

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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 {SiN Dipp} 2− dianion (SiN Dipp = {CH 2SiMe 2NDipp} 2; Dipp = 2,6-i-Pr 2C 6H 3) is intrinsic to the isolation of not only the group 1 alumanyl reagents ([{SiN Dipp}AlM] 2; M = K, Rb, Cs) but also facilitates the completely selective oxidative addition of a C-H bond of 1,2-C 2B 10H 12 to the aluminium centre. In each case, the resultant compounds comprise a four-coordinate o-carboranyl (hydrido)aluminate anion, [(SiN Dipp)Al(H)(1,2-C 2B 10H 11)] −, 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 + 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.",

keywords = "aluminium, bulky ligand, caesium, carborane, potassium, rubidium",

author = "Michael Hill and Han-Ying Liu and Pearce, {Kyle G.} and Mary Mahon",

year = "2024",

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doi = "10.3390/inorganics12120309",

language = "English",

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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 G.

AU - Mahon, Mary

PY - 2024/12/31

Y1 - 2024/12/31

N2 - The kinetic stability provided by the sterically demanding {SiN Dipp} 2− dianion (SiN Dipp = {CH 2SiMe 2NDipp} 2; Dipp = 2,6-i-Pr 2C 6H 3) is intrinsic to the isolation of not only the group 1 alumanyl reagents ([{SiN Dipp}AlM] 2; M = K, Rb, Cs) but also facilitates the completely selective oxidative addition of a C-H bond of 1,2-C 2B 10H 12 to the aluminium centre. In each case, the resultant compounds comprise a four-coordinate o-carboranyl (hydrido)aluminate anion, [(SiN Dipp)Al(H)(1,2-C 2B 10H 11)] −, 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 + 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.

AB - The kinetic stability provided by the sterically demanding {SiN Dipp} 2− dianion (SiN Dipp = {CH 2SiMe 2NDipp} 2; Dipp = 2,6-i-Pr 2C 6H 3) is intrinsic to the isolation of not only the group 1 alumanyl reagents ([{SiN Dipp}AlM] 2; M = K, Rb, Cs) but also facilitates the completely selective oxidative addition of a C-H bond of 1,2-C 2B 10H 12 to the aluminium centre. In each case, the resultant compounds comprise a four-coordinate o-carboranyl (hydrido)aluminate anion, [(SiN Dipp)Al(H)(1,2-C 2B 10H 11)] −, 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 + 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.

KW - aluminium

KW - bulky ligand

KW - caesium

KW - carborane

KW - potassium

KW - rubidium

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DO - 10.3390/inorganics12120309

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ER -

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

Abstract

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Alkaline Element Z-type Ligands for Tunable Base Metal Catalysis

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

Abstract

Data Availability Statement

Funding

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

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Alkaline Element Z-type Ligands for Tunable Base Metal Catalysis

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