DFT calculations have been used to probe the mechanism of the addition reaction of group 15 hydrides EH3 (E=N, P, As) and H2 to a N-heterocyclic silylene and its germylene homologue. Nitrogen lone pair donation into the vacant p-orbital of Si and Ge is the first step of ammonia activation, whereas silylene and germylene behave as nucleophiles toward dihydrogen, phosphane, and arsane. Formation of 1,4-addition products is kinetically favoured in all cases. In excess ammonia, the assistance of a second molecule drastically lowers the 1,1-addition energy barriers, enabling formation of 1,1-addition products. The participation of a second molecule in the PH bond activation of phosphane also lowers the 1,1-addition energy barriers, but not enough to cause inversion.

EH3 (E=N, P, As) and H2 Activation with N-Heterocyclic Silylene and Germylene Homologues

Alberto Marta Erminia;RUSSO, Nino;SICILIA, Emilia
2013

Abstract

DFT calculations have been used to probe the mechanism of the addition reaction of group 15 hydrides EH3 (E=N, P, As) and H2 to a N-heterocyclic silylene and its germylene homologue. Nitrogen lone pair donation into the vacant p-orbital of Si and Ge is the first step of ammonia activation, whereas silylene and germylene behave as nucleophiles toward dihydrogen, phosphane, and arsane. Formation of 1,4-addition products is kinetically favoured in all cases. In excess ammonia, the assistance of a second molecule drastically lowers the 1,1-addition energy barriers, enabling formation of 1,1-addition products. The participation of a second molecule in the PH bond activation of phosphane also lowers the 1,1-addition energy barriers, but not enough to cause inversion.
DENSITY-FUNCTIONAL THERMOCHEMISTRY,; MAIN-GROUP ELEMENTS; CARBENE
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/20.500.11770/138271
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