Innocent and less-innocent solvent ligands: a systematic investigation of cationic iron chloride/alcohol complexes by electrospray ionization mass spectrometry complemented by DFT calculations.
作者： Claudia Trage , Martin Diefenbach , Detlef Schröder , Helmut Schwarz
关键词: Ligand 、 Computational chemistry 、 Electrospray ionization 、 Molecule 、 Chemistry 、 Coordination sphere 、 Cationic polymerization 、 Reactivity (chemistry) 、 Inorganic chemistry 、 Solvent effects 、 Mass spectrometry
摘要: The influence of anionic and neutral ligands on the reactivity cationic iron complexes towards methanol, ethanol, iso- n-propanol has been investigated by means electrospray ionization (ESI) mass spectrometry, in key questions experimental results are supported DFT calculations. chemical processes taking place when FeCl2+ is coordinated to a variable number alcohol molecules were collision experiments, as well labeling studies. most abundant cations formed upon ESI FeCl3/ROH mixtures can be described consisting covalently bound core, which stabilized ROH ligands, for example, FeCl2(CH3OH)n+. Indications hydrogen-bonding mechanism second coordination sphere given observation formally hypercoordinated ion FeCl2(CH3OH)5+ interpretation kinetic data n=4. Further, deuterium experiments disclose hidden hydrogen transfers imply that with n=1 2 exist two tautomeric forms. Upon change ligand from methanol ethanol propanol, additional reaction pathways become accessible, among metal-assisted dehydration respective alcohols an ion/dipole important.
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