A mechanistic study of a topochemical dihydrogen to covalent bonding transformation

Radu Custelcean; James E. Jackson

doi:10.1016/S0040-6031(02)00023-0

A mechanistic study of a topochemical dihydrogen to covalent bonding transformation

Radu Custelcean, James E. Jackson

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

5 Scopus citations

Abstract

Solid-state decomposition of the dihydrogen-bonded complex LiBH₄·TEA (TEA: triethanolamine) into a covalent material was probed via ¹¹B MAS NMR and FT-IR spectroscopies, as well as single-crystal and powder X-ray diffraction and optical microscopy. Based on variable-temperature kinetic analysis and H/D exchange experiments, H₂ loss appears to occur via rate-limiting proton transfer from the TEA's-OH groups to the BH₄^- anions at the reactant/product interface. The activation parameters ΔH = 84 ± 10 kJ/mol and ΔS = -70 ± 26 J/(mol K) are comparable to those found for neutral aqueous hydrolysis of BH₄^-, suggesting similar mechanisms for the solid and solution decompositions.

Original language	English
Pages (from-to)	143-150
Number of pages	8
Journal	Thermochimica Acta
Volume	388
Issue number	1-2
DOIs	https://doi.org/10.1016/S0040-6031(02)00023-0
State	Published - Jun 18 2002
Externally published	Yes

Keywords

Borohydrides
Dihydrogen bonding
Solid-state NMR
Solid-state kinetics
Topochemical reactions

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10.1016/S0040-6031(02)00023-0

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title = "A mechanistic study of a topochemical dihydrogen to covalent bonding transformation",

abstract = "Solid-state decomposition of the dihydrogen-bonded complex LiBH4·TEA (TEA: triethanolamine) into a covalent material was probed via 11B MAS NMR and FT-IR spectroscopies, as well as single-crystal and powder X-ray diffraction and optical microscopy. Based on variable-temperature kinetic analysis and H/D exchange experiments, H2 loss appears to occur via rate-limiting proton transfer from the TEA's-OH groups to the BH4- anions at the reactant/product interface. The activation parameters ΔH = 84 ± 10 kJ/mol and ΔS = -70 ± 26 J/(mol K) are comparable to those found for neutral aqueous hydrolysis of BH4-, suggesting similar mechanisms for the solid and solution decompositions.",

keywords = "Borohydrides, Dihydrogen bonding, Solid-state NMR, Solid-state kinetics, Topochemical reactions",

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T1 - A mechanistic study of a topochemical dihydrogen to covalent bonding transformation

AU - Custelcean, Radu

AU - Jackson, James E.

PY - 2002/6/18

Y1 - 2002/6/18

N2 - Solid-state decomposition of the dihydrogen-bonded complex LiBH4·TEA (TEA: triethanolamine) into a covalent material was probed via 11B MAS NMR and FT-IR spectroscopies, as well as single-crystal and powder X-ray diffraction and optical microscopy. Based on variable-temperature kinetic analysis and H/D exchange experiments, H2 loss appears to occur via rate-limiting proton transfer from the TEA's-OH groups to the BH4- anions at the reactant/product interface. The activation parameters ΔH = 84 ± 10 kJ/mol and ΔS = -70 ± 26 J/(mol K) are comparable to those found for neutral aqueous hydrolysis of BH4-, suggesting similar mechanisms for the solid and solution decompositions.

AB - Solid-state decomposition of the dihydrogen-bonded complex LiBH4·TEA (TEA: triethanolamine) into a covalent material was probed via 11B MAS NMR and FT-IR spectroscopies, as well as single-crystal and powder X-ray diffraction and optical microscopy. Based on variable-temperature kinetic analysis and H/D exchange experiments, H2 loss appears to occur via rate-limiting proton transfer from the TEA's-OH groups to the BH4- anions at the reactant/product interface. The activation parameters ΔH = 84 ± 10 kJ/mol and ΔS = -70 ± 26 J/(mol K) are comparable to those found for neutral aqueous hydrolysis of BH4-, suggesting similar mechanisms for the solid and solution decompositions.

KW - Borohydrides

KW - Dihydrogen bonding

KW - Solid-state NMR

KW - Solid-state kinetics

KW - Topochemical reactions

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DO - 10.1016/S0040-6031(02)00023-0

M3 - Article

AN - SCOPUS:0037129868

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EP - 150

JO - Thermochimica Acta

JF - Thermochimica Acta

IS - 1-2

ER -

A mechanistic study of a topochemical dihydrogen to covalent bonding transformation

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Keywords

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