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EH 3 (E=N, P, As) and H 2 Activation with N‐Heterocyclic Silylene and Germylene Homologues
Author(s) -
Alberto Marta Erminia,
Russo Nino,
Sicilia Emilia
Publication year - 2013
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201203736
Subject(s) - silylene , chemistry , nucleophile , lone pair , molecule , activation energy , ammonia , antimony , activation barrier , medicinal chemistry , stereochemistry , crystallography , photochemistry , silicon , inorganic chemistry , catalysis , organic chemistry
Abstract DFT calculations have been used to probe the mechanism of the addition reaction of group 15 hydrides EH 3 (E=N, P, As) and H 2 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.