Synthesis of a Stable Adduct of Dialane(4) (Al2H4) Via Hydrogenation of a Magnesium(I) Dimer

Overview

Journal Nat Chem

Specialty Chemistry

Date 2010 Sep 24

PMID 20861903

Citations 16

Authors

Simon J Bonyhady

David Collis

Gernot Frenking

Nicole Holzmann

Cameron Jones

Andreas Stasch

Affiliations

Soon will be listed here.

Abstract

The desorption of dihydrogen from magnesium(II) hydride, MgH2 (containing 7.6 wt% H), is reversible. MgH2 therefore holds promise as a hydrogen storage material in devices powered by fuel cells. We believed that dimeric magnesium(I) dimers (LMgMgL, L=β-diketiminate) could find use as soluble models to aid the study of the mechanisms and/or kinetics of the hydrogenation of magnesium and its alloys. Here, we show that LMgMgL can be readily hydrogenated to yield LMg(µ-H)2MgL by treatment with aluminium(III) hydride complexes. In one case, hydrogenation was reversed by treating LMg(µ-H)2MgL with potassium metal. The hydrogenation by-products are the first thermally stable, neutral aluminium(II) hydride complexes to be produced, one of which, [{(IPr)(H)2Al}2] (IPr=:C[{(C6H3-i-Pr(2)-2,6)NCH}2]), is an N-heterocyclic carbene adduct of the elusive parent dialane4 (Al2H4). A computational analysis of this compound is presented.

Citing Articles

Nucleophilicity at copper(-I) in a compound with a Cu-Mg bond.

Jackson R, Evans N, Babula D, Downie T, Charman R, Neale S Nat Commun. 2025; 16(1):1101.

PMID: 39875432 PMC: 11775243. DOI: 10.1038/s41467-025-56544-z.

Electricity-driven organic hydrogenation using water as the hydrogen source.

Kundu B, Sun Y Chem Sci. 2024; .

PMID: 39371462 PMC: 11450802. DOI: 10.1039/d4sc03836c.

Reductive Coupling of a Diazoalkane Derivative Promoted by a Potassium Aluminyl and Elimination of Dinitrogen to Generate a Reactive Aluminium Ketimide.

Evans M, Anker M, McMullin C, Coles M Chemistry. 2023; 29(71):e202302903.

PMID: 37786384 PMC: 10946750. DOI: 10.1002/chem.202302903.

Stepwise reduction of a base-stabilised ferrocenyl aluminium(iii) dihalide for the synthesis of structurally-diverse dialane species.

Dhara D, Fantuzzi F, Harterich M, Dewhurst R, Krummenacher I, Arrowsmith M Chem Sci. 2022; 13(33):9693-9700.

PMID: 36091914 PMC: 9400590. DOI: 10.1039/d2sc02783f.

Generation of a transient base-stabilised arylalumylene for the facile deconstruction of aromatic molecules.

Dhara D, Jayaraman A, Harterich M, Dewhurst R, Braunschweig H Chem Sci. 2022; 13(19):5631-5638.

PMID: 35694334 PMC: 9116349. DOI: 10.1039/d2sc01436j.

References

Green S, Jones C, Stasch A . Stable magnesium(I) compounds with Mg-Mg bonds. Science. 2007; 318(5857):1754-7. DOI: 10.1126/science.1150856. View

Sidiropoulos A, Jones C, Stasch A, Klein S, Frenking G . N-heterocyclic carbene stabilized digermanium(0). Angew Chem Int Ed Engl. 2009; 48(51):9701-4. DOI: 10.1002/anie.200905495. View

Green S, Jones C, Stasch A . Stable adducts of a dimeric magnesium(I) compound. Angew Chem Int Ed Engl. 2008; 47(47):9079-83. DOI: 10.1002/anie.200803960. View

Hanada N, Ichikawa T, Fujii H . Catalytic effect of nanoparticle 3d-transition metals on hydrogen storage properties in magnesium hydride MgH2 prepared by mechanical milling. J Phys Chem B. 2006; 109(15):7188-94. DOI: 10.1021/jp044576c. View

Tonner R, Frenking G . Divalent carbon(0) chemistry, part 2: Protonation and complexes with main group and transition metal Lewis acids. Chemistry. 2008; 14(11):3273-89. DOI: 10.1002/chem.200701392. View

Ciobanu O, Kaifer E, Enders M, Himmel H . Synthesis of a stable B2H5(+) analogue by protonation of a double base-stabilized diborane(4). Angew Chem Int Ed Engl. 2009; 48(30):5538-41. DOI: 10.1002/anie.200901842. View

Aldridge S, Downs A . Hydrides of the main-group metals: new variations on an old theme. Chem Rev. 2002; 101(11):3305-65. DOI: 10.1021/cr960151d. View

Grochala W, Edwards P . Thermal decomposition of the non-interstitial hydrides for the storage and production of hydrogen. Chem Rev. 2004; 104(3):1283-316. DOI: 10.1021/cr030691s. View

Graetz J . New approaches to hydrogen storage. Chem Soc Rev. 2008; 38(1):73-82. DOI: 10.1039/b718842k. View

10.

Wang X, Andrews L, Tam S, DeRose M, Fajardo M . Infrared spectra of aluminum hydrides in solid hydrogen: Al2H4 and Al2H6. J Am Chem Soc. 2004; 125(30):9218-28. DOI: 10.1021/ja0353560. View

11.

Nogai S, Schmidbaur H . Dichlorogallane (HGaCl(2))(2): its molecular structure and synthetic potential. Inorg Chem. 2002; 41(18):4770-4. DOI: 10.1021/ic0203015. View

12.

Larsson P, Araujo C, Larsson J, Jena P, Ahuja R . Role of catalysts in dehydrogenation of MgH2 nanoclusters. Proc Natl Acad Sci U S A. 2008; 105(24):8227-31. PMC: 2448819. DOI: 10.1073/pnas.0711743105. View

13.

Bonyhady S, Jones C, Nembenna S, Stasch A, Edwards A, McIntyre G . Beta-diketiminate-stabilized magnesium(I) dimers and magnesium(II) hydride complexes: synthesis, characterization, adduct formation, and reactivity studies. Chemistry. 2009; 16(3):938-55. DOI: 10.1002/chem.200902425. View

14.

Wang Y, Xie Y, Wei P, King R, Schaefer 3rd H, von R Schleyer P . A stable silicon(0) compound with a Si=Si double bond. Science. 2008; 321(5892):1069-71. DOI: 10.1126/science.1160768. View

15.

Cole M, Jones C, Junk P, Kloth M, Stasch A . Synthesis and characterization of thermally robust amidinato group 13 hydride complexes. Chemistry. 2005; 11(15):4482-91. DOI: 10.1002/chem.200500278. View

16.

Wang Y, Quillian B, Wei P, Wannere C, Xie Y, King R . A stable, neutral diborene containing a B=B double bond. J Am Chem Soc. 2007; 129(41):12412-3. DOI: 10.1021/ja075932i. View

17.

Bonyhady S, Green S, Jones C, Nembenna S, Stasch A . A dimeric magnesium(I) compound as a facile two-center/two-electron reductant. Angew Chem Int Ed Engl. 2009; 48(16):2973-7. DOI: 10.1002/anie.200900331. View

18.

Schuth F, Bogdanovic B, Felderhoff M . Light metal hydrides and complex hydrides for hydrogen storage. Chem Commun (Camb). 2004; (20):2249-58. DOI: 10.1039/b406522k. View

19.

Jones C, McDyre L, Murphy D, Stasch A . Magnesium(I) reduction of benzophenone and anthracene: first structural characterisation of a magnesium ketyl. Chem Commun (Camb). 2010; 46(9):1511-3. DOI: 10.1039/b922002j. View

20.

Andrews L, Wang X . The infrared spectrum of Al2H6 in solid hydrogen. Science. 2003; 299(5615):2049-52. DOI: 10.1126/science.1082456. View