Synthesis and Reactivity of Alkali Metal Hydrido-Magnesiate Complexes which Exhibit Group 1 Metal Counter-Cation Specific Stability

Matthew J. Evans; Cameron Jones

doi:10.1021/acs.inorgchem.3c02086

Synthesis and Reactivity of Alkali Metal Hydrido-Magnesiate Complexes which Exhibit Group 1 Metal Counter-Cation Specific Stability

Matthew J. Evans, Cameron Jones

School of Chemistry

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

5 Citations (Scopus)

Abstract

Reactions of the series of alkali metal amides M(HMDS) (M = Li-Cs; HMDS = [N(SiMe₃)₂]⁻) with the neutral magnesium(II) hydride compound [Mg(BDI^Dipp)(μ-H)]₂ (BDI^Dipp = [CH{C(Me)NDipp}₂], Dipp = 2,6-ⁱPr₂-C₆H₃) have been carried out. When M = Li or Na, the reactions yielded Mg(BDI^Dipp)(HMDS) and MH as the primary products. In the sodium amide reaction, [Na₂(HMDS)][{Mg(BDI^Dipp)}₂(H)₃] was obtained as a low-yield by-product. When M = K-Cs, the reactions gave the group 1 metal hydrido-magnesiates, M₂[Mg(BDI^Dipp)(HMDS)(H)]₂·(benzene)_n (n = 0 or 1), the thermal stability of which increases with the increasing molecular weight of the alkali metal involved. Reactions of Cs₂[Mg(BDI^Dipp)(HMDS)(H)]₂·(benzene) with 18-crown-6 and CO gave the first monomeric alkali metal hydrido-magnesiate [Cs(18-crown-6)][Mg(BDI^Dipp)(HMDS)(H)] and the ethenediolate complex Cs₂[{Mg(BDI^Dipp)(HMDS)}₂(μ-C₂H₂O₂)], respectively. The new synthetic route to alkali metal hydrido-magnesiates described herein may facilitate further reactivity studies of this rare compound class.

Original language	English
Journal	Inorganic Chemistry
Volume	62
Issue number	35
DOIs	https://doi.org/10.1021/acs.inorgchem.3c02086
Publication status	Published - 21 Aug 2023

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@article{bcd9716b63ac45ff898f87fa7f850994,

title = "Synthesis and Reactivity of Alkali Metal Hydrido-Magnesiate Complexes which Exhibit Group 1 Metal Counter-Cation Specific Stability",

abstract = "Reactions of the series of alkali metal amides M(HMDS) (M = Li-Cs; HMDS = [N(SiMe3)2]−) with the neutral magnesium(II) hydride compound [Mg(BDIDipp)(μ-H)]2 (BDIDipp = [CH{C(Me)NDipp}2], Dipp = 2,6-iPr2-C6H3) have been carried out. When M = Li or Na, the reactions yielded Mg(BDIDipp)(HMDS) and MH as the primary products. In the sodium amide reaction, [Na2(HMDS)][{Mg(BDIDipp)}2(H)3] was obtained as a low-yield by-product. When M = K-Cs, the reactions gave the group 1 metal hydrido-magnesiates, M2[Mg(BDIDipp)(HMDS)(H)]2·(benzene)n (n = 0 or 1), the thermal stability of which increases with the increasing molecular weight of the alkali metal involved. Reactions of Cs2[Mg(BDIDipp)(HMDS)(H)]2·(benzene) with 18-crown-6 and CO gave the first monomeric alkali metal hydrido-magnesiate [Cs(18-crown-6)][Mg(BDIDipp)(HMDS)(H)] and the ethenediolate complex Cs2[{Mg(BDIDipp)(HMDS)}2(μ-C2H2O2)], respectively. The new synthetic route to alkali metal hydrido-magnesiates described herein may facilitate further reactivity studies of this rare compound class.",

author = "Evans, {Matthew J.} and Cameron Jones",

note = "Funding Information: C.J. thanks the Australian Research Council for funding. Moreover, this material is based upon work supported by the Air Force Office of Scientific Research under award number FA2386-21-1-4048. Publisher Copyright: {\textcopyright} 2023 American Chemical Society.",

year = "2023",

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doi = "10.1021/acs.inorgchem.3c02086",

language = "English",

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T1 - Synthesis and Reactivity of Alkali Metal Hydrido-Magnesiate Complexes which Exhibit Group 1 Metal Counter-Cation Specific Stability

AU - Evans, Matthew J.

AU - Jones, Cameron

N1 - Funding Information: C.J. thanks the Australian Research Council for funding. Moreover, this material is based upon work supported by the Air Force Office of Scientific Research under award number FA2386-21-1-4048. Publisher Copyright: © 2023 American Chemical Society.

PY - 2023/8/21

Y1 - 2023/8/21

N2 - Reactions of the series of alkali metal amides M(HMDS) (M = Li-Cs; HMDS = [N(SiMe3)2]−) with the neutral magnesium(II) hydride compound [Mg(BDIDipp)(μ-H)]2 (BDIDipp = [CH{C(Me)NDipp}2], Dipp = 2,6-iPr2-C6H3) have been carried out. When M = Li or Na, the reactions yielded Mg(BDIDipp)(HMDS) and MH as the primary products. In the sodium amide reaction, [Na2(HMDS)][{Mg(BDIDipp)}2(H)3] was obtained as a low-yield by-product. When M = K-Cs, the reactions gave the group 1 metal hydrido-magnesiates, M2[Mg(BDIDipp)(HMDS)(H)]2·(benzene)n (n = 0 or 1), the thermal stability of which increases with the increasing molecular weight of the alkali metal involved. Reactions of Cs2[Mg(BDIDipp)(HMDS)(H)]2·(benzene) with 18-crown-6 and CO gave the first monomeric alkali metal hydrido-magnesiate [Cs(18-crown-6)][Mg(BDIDipp)(HMDS)(H)] and the ethenediolate complex Cs2[{Mg(BDIDipp)(HMDS)}2(μ-C2H2O2)], respectively. The new synthetic route to alkali metal hydrido-magnesiates described herein may facilitate further reactivity studies of this rare compound class.

AB - Reactions of the series of alkali metal amides M(HMDS) (M = Li-Cs; HMDS = [N(SiMe3)2]−) with the neutral magnesium(II) hydride compound [Mg(BDIDipp)(μ-H)]2 (BDIDipp = [CH{C(Me)NDipp}2], Dipp = 2,6-iPr2-C6H3) have been carried out. When M = Li or Na, the reactions yielded Mg(BDIDipp)(HMDS) and MH as the primary products. In the sodium amide reaction, [Na2(HMDS)][{Mg(BDIDipp)}2(H)3] was obtained as a low-yield by-product. When M = K-Cs, the reactions gave the group 1 metal hydrido-magnesiates, M2[Mg(BDIDipp)(HMDS)(H)]2·(benzene)n (n = 0 or 1), the thermal stability of which increases with the increasing molecular weight of the alkali metal involved. Reactions of Cs2[Mg(BDIDipp)(HMDS)(H)]2·(benzene) with 18-crown-6 and CO gave the first monomeric alkali metal hydrido-magnesiate [Cs(18-crown-6)][Mg(BDIDipp)(HMDS)(H)] and the ethenediolate complex Cs2[{Mg(BDIDipp)(HMDS)}2(μ-C2H2O2)], respectively. The new synthetic route to alkali metal hydrido-magnesiates described herein may facilitate further reactivity studies of this rare compound class.

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U2 - 10.1021/acs.inorgchem.3c02086

DO - 10.1021/acs.inorgchem.3c02086

M3 - Article

C2 - 37602922

AN - SCOPUS:85169711873

SN - 0020-1669

VL - 62

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 35

ER -

Synthesis and Reactivity of Alkali Metal Hydrido-Magnesiate Complexes which Exhibit Group 1 Metal Counter-Cation Specific Stability

Abstract

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