Intermetallic Competition in the Fragmentation of Trimetallic Au-Zn-Alkali Complexes.
Johannes LangMerve CayirSimon P WalgPatrick Di Martino-FumoWerner R ThielGereon Niedner-SchatteburgPublished in: Chemistry (Weinheim an der Bergstrasse, Germany) (2016)
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 [AuZnCl3 ] with alkali metal ions (M(+) ) and investigate the charged adducts [AuZnCl3 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 ZnCl2 , whereas the K(+) , Rb(+) , and Cs(+) adducts preferably split off MCl2 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 MCl2 ZnCl rather than of MCl and ZnCl2 .
Keyphrases
- density functional theory
- transition metal
- mass spectrometry
- molecular dynamics
- ms ms
- genome wide
- quantum dots
- heavy metals
- healthcare
- single cell
- water soluble
- case control
- multiple sclerosis
- high glucose
- oxidative stress
- ion batteries
- hiv infected
- liquid chromatography
- high resolution
- risk assessment
- highly efficient
- electron transfer
- resting state
- crystal structure
- endothelial cells
- sensitive detection
- ionic liquid
- aqueous solution
- high performance liquid chromatography
- health information
- dna binding
- drug induced
- capillary electrophoresis
- functional connectivity