Reversible M−M Bonding by Alkaline Earth Metals (Mg, Ca, Sr, Ba) in Graphite Intercalation Compounds

Xu, Wei; Kozma, Karoly; Sha, Tianxiang; Wu, Yi‐Jen; Nyman, May; Lerner, Michael M.

doi:10.1002/chem.202000504

Title: Reversible M−M Bonding by Alkaline Earth Metals (Mg, Ca, Sr, Ba) in Graphite Intercalation Compounds

Journal Article · Tue Jun 02 00:00:00 EDT 2020 · Chemistry - A European Journal

DOI:https://doi.org/10.1002/chem.202000504· OSTI ID:1631493

Xu, Wei ^[1]; Kozma, Karoly ^[1]; Sha, Tianxiang ^[1]; Wu, Yi‐Jen ^[1];

^[1];

^[1]

Department of Chemistry Oregon State University Corvallis Oregon 97331-4003 United States

Abstract The alkaline earth metals (M=Mg, Ca, Sr, and Ba) exhibit a +2 oxidation state in nearly all known stable compounds, but M ^I dimeric complexes with M−M bonding, [M ₂ (en) ₂ ] ²⁺ , (en=ethylenediamine) of all these metals can be stabilized within the galleries of donor‐type graphite intercalation compounds (GICs). These metals can also form GICs with more conventional metal (II) ion complexes, [M(en) ₂ ] ²⁺ . Here, the facile interconversion between dimeric‐M ^I and monomeric‐M ^II intercalates upon the addition/removal of en are reported. Thermogravimetry, powder X‐ray diffraction, and pair distribution function analysis of total scattering data support the presence of either [M ₂ (en) ₂ ] ²⁺ or [M(en) ₂ ] ²⁺ guests. This phase conversion requires coupling graphene and metal redox centers, with associated reversible M−M bond formation within graphene galleries. This chemistry allows the facile isolation of unusual oxidation states, reveals M ⁰ →M ²⁺ reaction pathways, and present new opportunities in the design of hybrid conversion/intercalation materials for applications such as charge storage.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: DE SC0010802

OSTI ID:: 1631493

Journal Information:: Chemistry - A European Journal, Journal Name: Chemistry - A European Journal Vol. 26 Journal Issue: 36; ISSN 0947-6539

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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Cited by: 2 works

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