Structures of XH 4 + and XH 6 + (X = B, Al and Ga) Cations

Salzbrunn, Stefan; Rasul, Golam; Prakash, G. K. Surya; Oláh, George A.

doi:10.1007/s0089400060213

Cited by 5 publications

(1 citation statement)

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“…In addition, these authors also reported some reactions involving deuterium labeled reactants (BD 2 + and/or labeled neutrals) that showed some insights on the reaction mechanisms. Furthermore, the reaction of BH 2 + with an excess of H 2 was shown , to produce BH 6 + , a structure isoelectronic with CH 6 2+ containing two three-center two-electron (3c−2e) bonds, which was the focus of substantial theoretical interest. , However, one of the main conclusions of these experiments was the observation that BH 2 + can activate C−H and C−C bonds in hydrocarbons very efficiently, something that was thought to be just in the realm of transition metal cation chemistry , and of central importance in catalysis. The chemistry of BH 2 + was found analogous to that of CH 3 + , despite BH 2 + being isoelectronic with CH 2 2+ ; however, these experiments and theoretical results suggest significant differences in their reactivities, consistent with a lower electrophilicity and increased selectivity of BH 2 + .…”

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confidence: 99%

Computational Study of the Reactions of BH₂⁺ with H₂, Methane, Ethane, Ethylene, and Acetylene in the Gas Phase

Zeng

Davico

2003

J. Phys. Chem. A

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We have studied the potential energy surface for the reactions of BH 2 + with H 2 , methane, ethylene and acetylene at the CCSD(T)/cc-pVTZ//MP2(full)/cc-pVTZ level and the reaction of BH 2 + with ethane at the CCSD(T)/ 6-311G(d,p)//MP2(full)/6-311G(d,p) level of theory. A complete survey of the potential energy surfaces is presented and the structures of the stationary points and the mechanisms of these reactions are discussed. The calculations suggest that the products of these reactions are formed by addition and elimination of a hydrogen molecule, effectively activating the carbon-hydrogen bond. Furthermore, theory also suggests that elimination of HD is the sole product in the reaction of BD 2 + with ethane; however, H/D scrambling occurs to some extent in the reaction with acetylene whereas it is complete in the reaction with ethylene. Therefore, loss of H 2 , HD, and D 2 is predicted, in agreement with experiments. In addition, elimination of CH 4 can also be produced in the reaction of BH 2 + with ethane, even with BD 2 + as reactant. Although the products of the carbon-carbon bond activation are also exothermic in the reactions of acetylene and ethylene, they are prevented kinetically. The remarkable electrophilic properties of BH 2 + are presented and discussed as well as details on the bonding structure of the three-center two-electron bonds characteristic of these compounds.

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