Hydrocarbon soluble alkali-metal-aluminium hydride surrog[ATES]

Sumanta Banerjee; Peter A. MacDonald; Samantha A. Orr; Alan R. Kennedy; Alexander van Teijlingen; Stuart D. Robertson; Tell Tuttle; Robert E. Mulvey

doi:10.1002/chem.202201085

Hydrocarbon soluble alkali-metal-aluminium hydride surrog[ATES]

Sumanta Banerjee, Peter A. MacDonald, Samantha A. Orr, Alan R. Kennedy, Alexander van Teijlingen, Stuart D. Robertson, Tell Tuttle, Robert E. Mulvey

Pure And Applied Chemistry

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Abstract

A series of group 1 hydrocarbon-soluble donor free aluminates [AM( ^tBuDHP)(TMP)Al( ⁱBu) ₂] (AM=Li, Na, K, Rb) have been synthesised by combining an alkali metal dihydropyridyl unit [(2- ^tBuC ₅H ₅N)AM)] containing a surrogate hydride (sp ³ C−H) with [( ⁱBu) ₂Al(TMP)]. These aluminates have been characterised by X-ray crystallography and NMR spectroscopy. While the lithium aluminate forms a monomer, the heavier alkali metal aluminates exist as polymeric chains propagated by non-covalent interactions between the alkali metal cations and the alkyldihydropyridyl units. Solvates [(THF)Li( ^tBuDHP)(TMP)Al( ⁱBu) ₂] and [(TMEDA)Na( ^tBuDHP)(TMP)Al( ⁱBu) ₂] have also been crystallographically characterised. Theoretical calculations show how the dispersion forces tend to increase on moving from Li to Rb, as opposed to the electrostatic forces of stabilization, which are orders of magnitude more significant. Having unique structural features, these bimetallic compounds can be considered as starting points for exploring unique reactivity trends as alkali-metal-aluminium hydride surrog[ATES].

Original language	English
Number of pages	13
Journal	Chemistry - A European Journal
Volume	28
Issue number	55
Early online date	10 Jul 2022
DOIs	https://doi.org/10.1002/chem.202201085
Publication status	Published - 4 Oct 2022

Keywords

alkali metal aluminates
hydrides
dihydropyridine
heterobimetallic complexes
London dispersion forces

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10.1002/chem.202201085Licence: CC BY 4.0

Banerjee-etal-CAEJ-2022-Hydrocarbon-soluble-Alkali-metal-aluminiumFinal published version, 1.64 MBLicence: CC BY 4.0

Propelling Sodium to the Forefront of Metallation Chemistry
Mulvey, R. & Robertson, S.
Leverhulme Trust
1/04/20 → 31/03/24
Project: Research

Data for: "Hydrocarbon soluble alkali-metal-aluminium hydride surrog[ATES]"
Banerjee, S. (Contributor), MacDonald, P. A. (Contributor), Kennedy, A. (Contributor), van Teijlingen, A. (Contributor), Robertson, S. (Contributor), Tuttle, T. (Contributor) & Mulvey, R. (Creator), University of Strathclyde, 1 Aug 2022
DOI: 10.15129/624adb63-0e47-406d-a288-7bb035a027e3
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@article{b5152fe46bed4776bcd6fb85f24345d0,

title = "Hydrocarbon soluble alkali-metal-aluminium hydride surrog[ATES]",

abstract = "A series of group 1 hydrocarbon-soluble donor free aluminates [AM( tBuDHP)(TMP)Al( iBu) 2] (AM=Li, Na, K, Rb) have been synthesised by combining an alkali metal dihydropyridyl unit [(2- tBuC 5H 5N)AM)] containing a surrogate hydride (sp 3 C−H) with [( iBu) 2Al(TMP)]. These aluminates have been characterised by X-ray crystallography and NMR spectroscopy. While the lithium aluminate forms a monomer, the heavier alkali metal aluminates exist as polymeric chains propagated by non-covalent interactions between the alkali metal cations and the alkyldihydropyridyl units. Solvates [(THF)Li( tBuDHP)(TMP)Al( iBu) 2] and [(TMEDA)Na( tBuDHP)(TMP)Al( iBu) 2] have also been crystallographically characterised. Theoretical calculations show how the dispersion forces tend to increase on moving from Li to Rb, as opposed to the electrostatic forces of stabilization, which are orders of magnitude more significant. Having unique structural features, these bimetallic compounds can be considered as starting points for exploring unique reactivity trends as alkali-metal-aluminium hydride surrog[ATES]. ",

keywords = "alkali metal aluminates, hydrides, dihydropyridine, heterobimetallic complexes, London dispersion forces",

author = "Sumanta Banerjee and MacDonald, {Peter A.} and Orr, {Samantha A.} and Kennedy, {Alan R.} and {van Teijlingen}, Alexander and Robertson, {Stuart D.} and Tell Tuttle and Mulvey, {Robert E.}",

year = "2022",

month = oct,

day = "4",

doi = "10.1002/chem.202201085",

language = "English",

volume = "28",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

number = "55",

}

TY - JOUR

T1 - Hydrocarbon soluble alkali-metal-aluminium hydride surrog[ATES]

AU - Banerjee, Sumanta

AU - MacDonald, Peter A.

AU - Orr, Samantha A.

AU - Kennedy, Alan R.

AU - van Teijlingen, Alexander

AU - Robertson, Stuart D.

AU - Tuttle, Tell

AU - Mulvey, Robert E.

PY - 2022/10/4

Y1 - 2022/10/4

N2 - A series of group 1 hydrocarbon-soluble donor free aluminates [AM( tBuDHP)(TMP)Al( iBu) 2] (AM=Li, Na, K, Rb) have been synthesised by combining an alkali metal dihydropyridyl unit [(2- tBuC 5H 5N)AM)] containing a surrogate hydride (sp 3 C−H) with [( iBu) 2Al(TMP)]. These aluminates have been characterised by X-ray crystallography and NMR spectroscopy. While the lithium aluminate forms a monomer, the heavier alkali metal aluminates exist as polymeric chains propagated by non-covalent interactions between the alkali metal cations and the alkyldihydropyridyl units. Solvates [(THF)Li( tBuDHP)(TMP)Al( iBu) 2] and [(TMEDA)Na( tBuDHP)(TMP)Al( iBu) 2] have also been crystallographically characterised. Theoretical calculations show how the dispersion forces tend to increase on moving from Li to Rb, as opposed to the electrostatic forces of stabilization, which are orders of magnitude more significant. Having unique structural features, these bimetallic compounds can be considered as starting points for exploring unique reactivity trends as alkali-metal-aluminium hydride surrog[ATES].

AB - A series of group 1 hydrocarbon-soluble donor free aluminates [AM( tBuDHP)(TMP)Al( iBu) 2] (AM=Li, Na, K, Rb) have been synthesised by combining an alkali metal dihydropyridyl unit [(2- tBuC 5H 5N)AM)] containing a surrogate hydride (sp 3 C−H) with [( iBu) 2Al(TMP)]. These aluminates have been characterised by X-ray crystallography and NMR spectroscopy. While the lithium aluminate forms a monomer, the heavier alkali metal aluminates exist as polymeric chains propagated by non-covalent interactions between the alkali metal cations and the alkyldihydropyridyl units. Solvates [(THF)Li( tBuDHP)(TMP)Al( iBu) 2] and [(TMEDA)Na( tBuDHP)(TMP)Al( iBu) 2] have also been crystallographically characterised. Theoretical calculations show how the dispersion forces tend to increase on moving from Li to Rb, as opposed to the electrostatic forces of stabilization, which are orders of magnitude more significant. Having unique structural features, these bimetallic compounds can be considered as starting points for exploring unique reactivity trends as alkali-metal-aluminium hydride surrog[ATES].

KW - alkali metal aluminates

KW - hydrides

KW - dihydropyridine

KW - heterobimetallic complexes

KW - London dispersion forces

U2 - 10.1002/chem.202201085

DO - 10.1002/chem.202201085

M3 - Article

SN - 0947-6539

VL - 28

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 55

ER -

Hydrocarbon soluble alkali-metal-aluminium hydride surrog[ATES]

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