Please use this identifier to cite or link to this item: http://dx.doi.org/10.14279/depositonce-5282
Main Title: C-N coupling in the gas-phase reactions of ammonia and [M(CH)](+) (M = Ni, Pd, Pt): a combined experimental/computational exercise
Author(s): Kretschmer, Robert
Schlangen, Maria
Schwarz, Helmut
Type: Article
Language Code: en
Abstract: Electrospray ionization (ESI) of methanolic solutions of monomeric nickel(II) acetate, [Ni(CH3COO)2], and tetrameric platinum(II) acetate, [Pt4(CH3COO)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/[CH4N]+ and [M(CH2N)]+/H2 are observed for both metals, hydrogen-atom expulsion to generate [M(CHNH2)]+/H is only observed in the case of the nickel-containing system, and the proton transfer leading to M/[NH4]+ is limited to platinum. Attempts to conduct related experiments with [Pd(CH)]+/NH3 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)]+/NH3 and [M(CH)]+/ND3 (M = Ni, Pt), two different mechanistic scenarios of the dehydrogenation process are operative for the Ni and Pt systems, respectively.
URI: http://depositonce.tu-berlin.de/handle/11303/5662
http://dx.doi.org/10.14279/depositonce-5282
Issue Date: 2013
Date Available: 27-Jun-2016
DDC Class: 540 Chemie und zugeordnete Wissenschaften
Sponsor/Funder: DFG, EXC 314, Unifying Concepts in Catalysis
Usage rights: Terms of German Copyright Law
Journal Title: Dalton transactions : a journal of inorganic chemistry, including bioinorganic, organometallic, and solid-state chemistry
Publisher: Royal Society of Chemistry
Publisher Place: Cambridge
Volume: 42
Issue: 12
Publisher DOI: 10.1039/c3dt32596b
Page Start: 4153
Page End: 4162
EISSN: 1477-9226
Notes: Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich.
This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively.
Appears in Collections:Technische Universität Berlin » Fakultäten & Zentralinstitute » Fakultät 2 Mathematik und Naturwissenschaften » Institut für Chemie » Publications

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