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Thermal Activation of Ammonia by Transition‐Metal Hydroxide Cations
Author(s) -
Kretschmer Robert,
Schlangen Maria,
Schwarz Helmut
Publication year - 2013
Publication title -
chempluschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.801
H-Index - 61
ISSN - 2192-6506
DOI - 10.1002/cplu.201300138
Subject(s) - chemistry , ammonia , dehydrogenation , transition metal , adduct , hydroxide , ligand (biochemistry) , reaction mechanism , metathesis , inorganic chemistry , thermal decomposition , salt metathesis reaction , metal , medicinal chemistry , catalysis , organic chemistry , polymerization , biochemistry , polymer , receptor
With the exception of [Cu(OH)] + , the thermal reactions of the first‐row transition‐metal hydroxide cations, [Sc(OH)] + –[Zn(OH)] + , with ammonia have been studied by means of gas‐phase experiments and by computational methods for the whole series. The primary reaction channels involve NH bond activation, forming [M(NH 2 )] + concomitantly with the elimination of water, and adduct formation, leading to [M(OH)(NH 3 )] + . Furthermore, [Ti(OH)] + and [V(OH)] + react with ammonia under dehydrogenation conditions, leading to [M,O,N,H 2 ] + (M=Ti, V), and for [Ni(OH)] + ligand exchange is observed. Computations of the main reaction channels have been performed for the [M(OH)] + /NH 3 couples (M=Sc–Zn) to uncover the underlying reaction mechanism and periodic trends across the first row. For NH bond activation, σ‐bond metathesis was found to be the underlying mechanism.