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Intermetallic Competition in the Fragmentation of Trimetallic Au–Zn–Alkali Complexes
Author(s) -
Lang Johannes,
Cayir Merve,
Walg Simon P.,
Di MartinoFumo Patrick,
Thiel Werner R.,
NiednerSchatteburg Gereon
Publication year - 2016
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.201504093
Subject(s) - chemistry , alkali metal , dissociation (chemistry) , electrospray ionization , density functional theory , collision induced dissociation , infrared multiphoton dissociation , fragmentation (computing) , hsab theory , adduct , linkage isomerism , catalysis , mass spectrometry , ion , inorganic chemistry , computational chemistry , tandem mass spectrometry , metal , organic chemistry , chromatography , computer science , operating system
Cationization is a valuable tool to enable mass spectrometric studies on neutral transition‐metal complexes (e.g., homogenous catalysts). However, knowledge of potential impacts on the molecular structure and catalytic reactivity induced by the cationization is indispensable to extract information about the neutral complex. In this study, we cationize a bimetallic complex [AuZnCl 3 ] with alkali metal ions (M + ) and investigate the charged adducts [AuZnCl 3 M] + by electrospray ionization mass spectrometry (ESI‐MS). Infrared multiple photon dissociation (IR‐MPD) in combination with density functional theory (DFT) calculations reveal a μ 3 binding motif of all alkali ions to the three chlorido ligands. The cationization induces a reorientation of the organic backbone. Collision‐induced dissociation (CID) studies reveal switches of fragmentation channels by the alkali ion and by the CID amplitude. The Li + and Na + adducts prefer the sole loss of ZnCl 2 , whereas the K + , Rb + , and Cs + adducts preferably split off MCl 2 ZnCl. Calculated energetics along the fragmentation coordinate profiles allow us to interpret the experimental findings to a level of subtle details. The Zn 2+ cation wins the competition for the nitrogen coordination sites against K + , Rb + , and Cs + , but it loses against Li + and Na + in a remarkable deviation from a naive hard and soft acids and bases (HSAB) concept. The computations indicate expulsion of MCl 2 ZnCl rather than of MCl and ZnCl 2 .