Manganese borohydride; synthesis and characterization

Bo Richter, Dorthe B. Ravnsbæk, Nikolay Tumanov, Yaroslav Filinchuk, Torben René Jensen

Résultats de recherche: Contribution à un journal/une revueArticle

Résumé

Solvent-based synthesis and characterization of α-Mn(BH4)2 and a new nanoporous polymorph of manganese borohydride, γ-Mn(BH4)2, via a new solvate precursor, Mn(BH4)2·1/2S(CH3)2, is presented. Manganese chloride is reacted with lithium borohydride in a toluene/dimethylsulfide mixture at room temperature, which yields halide and solvent-free manganese borohydride after extraction with dimethylsulfide (DMS) and subsequent removal of residual solvent. This work constitutes the first example of establishing a successful, reproducible solvent-based synthesis route for a pure, crystalline, stable transition metal borohydride. The new polymorph, γ-Mn(BH4)2, is shown to be the manganese counterpart of the zeolite-like compound, γ-Mg(BH4)2 (cubic, a = 16.209(1) Å, space group Id3[combining macron]a). It is verified that large pores (diameter > 6.0 Å) exist in this structure. The solvate, Mn(BH4)2·1/2S(CH3)2, is subsequently shown to be the analogue of Mg(BH4)2·1/2S(CH3)2. As the structural analogies between Mg(BH4)2 and Mn(BH4)2 became evident a new polymorph of Mg(BH4)2 was identified and termed ζ-Mg(BH4)2. ζ-Mg(BH4)2 is the structural counterpart of α-Mn(BH4)2. All synthesis products are characterized employing synchrotron radiation-powder X-ray diffraction, infrared spectroscopy and thermogravimetric analysis in combination with mass spectroscopy. Thermal analysis reveals the decomposition of Mn(BH4)2 to occur at 160 °C, accompanied by a mass loss of 14.8 wt%. A small quantity of the desorbed gaseous species is identified as diborane (ρm(Mn(BH4)2) = 9.5 wt% H2), while the remaining majority is found to be hydrogen.
langue originaleAnglais
Pages (de - à)3988-3996
Nombre de pages9
journalDalton Transactions
Volume44
Numéro de publication9
Les DOIs
étatPublié - 22 janv. 2015
Modification externeOui

Empreinte digitale

Borohydrides
Manganese
Polymorphism
Zeolites
Toluene
Synchrotron radiation
X ray powder diffraction
Thermoanalysis
Transition metals
Thermogravimetric analysis
Hydrogen
Infrared spectroscopy
Spectroscopy
Crystalline materials
Decomposition
Temperature
dimethyl sulfide

Citer ceci

Richter, B., Ravnsbæk, D. B., Tumanov, N., Filinchuk, Y., & Jensen, T. R. (2015). Manganese borohydride; synthesis and characterization. Dalton Transactions, 44(9), 3988-3996. https://doi.org/10.1039/C4DT03501A
Richter, Bo ; Ravnsbæk, Dorthe B. ; Tumanov, Nikolay ; Filinchuk, Yaroslav ; Jensen, Torben René. / Manganese borohydride; synthesis and characterization. Dans: Dalton Transactions. 2015 ; Vol 44, Numéro 9. p. 3988-3996.
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abstract = "Solvent-based synthesis and characterization of α-Mn(BH4)2 and a new nanoporous polymorph of manganese borohydride, γ-Mn(BH4)2, via a new solvate precursor, Mn(BH4)2·1/2S(CH3)2, is presented. Manganese chloride is reacted with lithium borohydride in a toluene/dimethylsulfide mixture at room temperature, which yields halide and solvent-free manganese borohydride after extraction with dimethylsulfide (DMS) and subsequent removal of residual solvent. This work constitutes the first example of establishing a successful, reproducible solvent-based synthesis route for a pure, crystalline, stable transition metal borohydride. The new polymorph, γ-Mn(BH4)2, is shown to be the manganese counterpart of the zeolite-like compound, γ-Mg(BH4)2 (cubic, a = 16.209(1) {\AA}, space group Id3[combining macron]a). It is verified that large pores (diameter > 6.0 {\AA}) exist in this structure. The solvate, Mn(BH4)2·1/2S(CH3)2, is subsequently shown to be the analogue of Mg(BH4)2·1/2S(CH3)2. As the structural analogies between Mg(BH4)2 and Mn(BH4)2 became evident a new polymorph of Mg(BH4)2 was identified and termed ζ-Mg(BH4)2. ζ-Mg(BH4)2 is the structural counterpart of α-Mn(BH4)2. All synthesis products are characterized employing synchrotron radiation-powder X-ray diffraction, infrared spectroscopy and thermogravimetric analysis in combination with mass spectroscopy. Thermal analysis reveals the decomposition of Mn(BH4)2 to occur at 160 °C, accompanied by a mass loss of 14.8 wt{\%}. A small quantity of the desorbed gaseous species is identified as diborane (ρm(Mn(BH4)2) = 9.5 wt{\%} H2), while the remaining majority is found to be hydrogen.",
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Richter, B, Ravnsbæk, DB, Tumanov, N, Filinchuk, Y & Jensen, TR 2015, 'Manganese borohydride; synthesis and characterization', Dalton Transactions, VOL. 44, Numéro 9, p. 3988-3996. https://doi.org/10.1039/C4DT03501A

Manganese borohydride; synthesis and characterization. / Richter, Bo; Ravnsbæk, Dorthe B.; Tumanov, Nikolay; Filinchuk, Yaroslav; Jensen, Torben René.

Dans: Dalton Transactions, Vol 44, Numéro 9, 22.01.2015, p. 3988-3996.

Résultats de recherche: Contribution à un journal/une revueArticle

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T1 - Manganese borohydride; synthesis and characterization

AU - Richter, Bo

AU - Ravnsbæk, Dorthe B.

AU - Tumanov, Nikolay

AU - Filinchuk, Yaroslav

AU - Jensen, Torben René

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AB - Solvent-based synthesis and characterization of α-Mn(BH4)2 and a new nanoporous polymorph of manganese borohydride, γ-Mn(BH4)2, via a new solvate precursor, Mn(BH4)2·1/2S(CH3)2, is presented. Manganese chloride is reacted with lithium borohydride in a toluene/dimethylsulfide mixture at room temperature, which yields halide and solvent-free manganese borohydride after extraction with dimethylsulfide (DMS) and subsequent removal of residual solvent. This work constitutes the first example of establishing a successful, reproducible solvent-based synthesis route for a pure, crystalline, stable transition metal borohydride. The new polymorph, γ-Mn(BH4)2, is shown to be the manganese counterpart of the zeolite-like compound, γ-Mg(BH4)2 (cubic, a = 16.209(1) Å, space group Id3[combining macron]a). It is verified that large pores (diameter > 6.0 Å) exist in this structure. The solvate, Mn(BH4)2·1/2S(CH3)2, is subsequently shown to be the analogue of Mg(BH4)2·1/2S(CH3)2. As the structural analogies between Mg(BH4)2 and Mn(BH4)2 became evident a new polymorph of Mg(BH4)2 was identified and termed ζ-Mg(BH4)2. ζ-Mg(BH4)2 is the structural counterpart of α-Mn(BH4)2. All synthesis products are characterized employing synchrotron radiation-powder X-ray diffraction, infrared spectroscopy and thermogravimetric analysis in combination with mass spectroscopy. Thermal analysis reveals the decomposition of Mn(BH4)2 to occur at 160 °C, accompanied by a mass loss of 14.8 wt%. A small quantity of the desorbed gaseous species is identified as diborane (ρm(Mn(BH4)2) = 9.5 wt% H2), while the remaining majority is found to be hydrogen.

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Richter B, Ravnsbæk DB, Tumanov N, Filinchuk Y, Jensen TR. Manganese borohydride; synthesis and characterization. Dalton Transactions. 2015 janv. 22;44(9):3988-3996. https://doi.org/10.1039/C4DT03501A