NDLI: C–N coupling in the gas-phase reactions of ammonia and $[M(CH)]^{+}$ (M = Ni, Pd, Pt): a combined experimental/computational exercise

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Schlangen, Maria Schwarz, Helmut Kretschmer, Robert
Description	Author Affiliation: Kretschmer R ( Technische Universität Berlin, Institut für Chemie, Strasse des 17.Juni 115, 10623 Berlin, Germany.)
Abstract	Electrospray ionization (ESI) of methanolic solutions of monomeric nickel(II) acetate, $[Ni(CH_{3}COO)_{2}],$ and tetrameric platinum(II) acetate, $[Pt_{4}(CH_{3}COO)_{8}],$ leads to the formation of the corresponding methylidyne complexes $[M(CH)]^{+}$ (M = Ni, Pt), which react with ammonia under C–N coupling. While the product couples $M/[CH_{4}N]^{+}$ and $[M(CH_{2}N)]^{+}/H_{2}$ are observed for both metals, hydrogen-atom expulsion to generate $[M(CHNH_{2})]^{+}/H$ is only observed in the case of the nickel-containing system, and the proton transfer leading to $M/[NH_{4}]^{+}$ is limited to platinum. Attempts to conduct related experiments with $[Pd(CH)]^{+}/NH_{3}$ failed. The mechanisms that explain the experimentally observed reaction channels have been investigated computationally using the B3LYP functional for all metals of the nickel group (M = Ni, Pd, Pt). In line with labeling experiments using the reaction pairs $[M(CD)]^{+}/NH_{3}$ and $[M(CH)]^{+}/ND_{3}$ (M = Ni, Pt), two different mechanistic scenarios of the dehydrogenation process are operative for the Ni and Pt systems, respectively.
ISSN	14779226
Issue Number	12
Volume Number	42
e-ISSN	13645447
Journal	Dalton Trans.
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2013-03-28
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Ammonia Chemistry Coordination Complexes Gases Nickel Palladium Platinum Carbon Nitrogen Spectrometry, Mass, Electrospray Ionization Thermodynamics Journal Article Research Support, Non-U.S. Gov't
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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