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On the Electronic Origin of Remarkable Ligand Effects on the Reactivities of [NiL] + Complexes (L=C 6 H 5 , C 5 H 4 N, CN) towards Methane
Author(s) -
Zhou Shaodong,
Firouzbakht Marjan,
Schlangen Maria,
Kaupp Martin,
Schwarz Helmut
Publication year - 2017
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.201703767
Subject(s) - chemistry , ligand (biochemistry) , hydrogen , substrate (aquarium) , hydrogen atom , electron transfer , hydrogen atom abstraction , electrospray ionization , ionization , methane , proton , mass spectrometry , atom (system on chip) , crystallography , ion , physics , organic chemistry , biochemistry , oceanography , receptor , alkyl , chromatography , quantum mechanics , computer science , embedded system , geology
The gas‐phase reactions of [NiL] + (L=C 6 H 5 , C 5 H 4 N, CN) with methane have been explored by using electrospray‐ionization mass spectrometry (ESI‐MS) complemented by quantum chemical calculations. Though the phenyl Ni complex [Ni(C 6 H 5 )] + exclusively abstracts one hydrogen atom from methane at ambient conditions, the cyano Ni complex [Ni(CN)] + brings about both H‐atom abstraction and ligand exchange to generate [Ni(CH 3 )] + . In contrast, the complex 2‐pyridinyl Ni [Ni(C 5 H 4 N)] + is inert towards this substrate. The presence of the empty 4s(Ni) orbital dominates the proton‐coupled electron transfer (PCET) processes for the investigated systems.