2007
DOI: 10.1021/jp066175y
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Molecular Mechanism for H2 Release from BH3NH3, Including the Catalytic Role of the Lewis Acid BH3

Abstract: Electronic structure calculations using various methods, up to the coupled-cluster CCSD(T) level, in conjunction with the aug-cc-pVnZ basis sets with n = D, T, and Q, extrapolated to the complete basis set limit, show that the borane molecule (BH3) can act as an efficient bifunctional acid-base catalyst in the H2 elimination reactions of XHnYHn systems (X, Y = C, B, N). Such a catalyst is needed as the generation of H2 from isoelectronic ethane and borane amine compounds proceeds with an energy barrier much hi… Show more

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Cited by 164 publications
(267 citation statements)
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“…For a comparative analysis of reaction-energy barriers, calculations to determine the transition state (TS) without catalyst led to a gas-phase energy-barrier estimate for intramolecular dehydrogenation of AB of 37.04 kcal/mol; this is consistent with a value of 36.4 kcal/mol obtained at the CCSD(T)/CBS level of theory [4].…”
Section: Resultssupporting
confidence: 72%
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“…For a comparative analysis of reaction-energy barriers, calculations to determine the transition state (TS) without catalyst led to a gas-phase energy-barrier estimate for intramolecular dehydrogenation of AB of 37.04 kcal/mol; this is consistent with a value of 36.4 kcal/mol obtained at the CCSD(T)/CBS level of theory [4].…”
Section: Resultssupporting
confidence: 72%
“…There are many published theoretical and experimental studies on the dehydrogenation of ammonia-borane [3][4][5][6][7][8][9][10][11][12][13][14][15][16][17] in both solution as well as the solid state. These studies demonstrate that reactions featuring transition-metal and s-block metal-centered-complex catalysts facilitate an efficient lower-temperature release of hydrogen.…”
Section: Introductionmentioning
confidence: 99%
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“…The phenomenon is also well established for 4-center elimination reactions in BH 3 NH 3 and C 2 H 6 [46]. Intriguingly, the central D atom in 2MgH 2 + D 2 system is almost electroneutral and the stabilization is achieved mainly due to the electrostatic interactions between Mg and connected hydrogen atoms.…”
Section: Hat Mechanism In 'Gas-phase' Modelsmentioning
confidence: 67%
“…[36] The authors noted that while AB is isoelectronic with ethane, computational results [24,37] do not bear out this comparison in terms of reactivity, and that AB would be better compared to methanol in this regard. Further support for this comparison is the observation by Schneider that their ruthenium PNP complex demonstrated activity for the dehydrogenation of alcohols.…”
Section: New Catalyst Developmentsmentioning
confidence: 99%