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Reactivity Pattern in the Room‐Temperature Activation of NH 3 by the Main‐Group Atomic Ions Ga + , Ge + , As + and Se +
Author(s) -
Koyanagi Gregory K.,
Kapishon Vitaliy,
Bohme Diethard K.,
Zhang Xinhao,
Schwarz Helmut
Publication year - 2010
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200901126
Subject(s) - chemistry , reactivity (psychology) , ion , ammonia , kinetic energy , proton , activation energy , hydrogen , chemical kinetics , kinetics , hydrogen atom , yield (engineering) , inorganic chemistry , analytical chemistry (journal) , group (periodic table) , organic chemistry , quantum mechanics , medicine , physics , alternative medicine , materials science , pathology , metallurgy
The activation of ammonia by the main‐group cations Ga + , Ge + , As + and Se + has been explored both experimentally and theoretically. ICP/SIFT tandem mass spectrometer measurements of room‐temperature kinetics have revealed a substantial variation in rates and product distributions across the Periodic Table of Elements. The main features of the observed primary chemistry include H‐atom elimination, ammonia addition and a cation‐assisted proton transfer to yield NH 4 + that is second order in ammonia. These observations are shown to be completely consistent with computed potential energy surfaces for the reactions of each of the four atomic cations. Dehydrogenation by the elimination of molecular hydrogen, not observed experimentally, is shown by the calculations to be inhibited by the presence of a kinetic barrier.