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Solvent and Ligand Effects on the Structures of Iron Halide Cations in the Gas Phase
Author(s) -
Gruene Philipp,
Trage Claudia,
Schröder Detlef,
Schwarz Helmut
Publication year - 2006
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200600587
Subject(s) - chemistry , halide , bromine , ligand (biochemistry) , bromide , electrospray ionization , solvent , inorganic chemistry , cationic polymerization , molecule , ion , oxidation state , metal , crystallography , medicinal chemistry , organic chemistry , biochemistry , receptor
The effects of the oxidation state, the ligand, and the solvent on structures and energetics of cationic iron complexes are investigated by means of electrospray‐ionization mass spectrometry. Insights into the potential‐energy surfaces of FeX + , FeX 2 + , and XFe(OCH 3 ) + ions (X = F, Cl, Br, I) with a variable number of coordinated methanol molecules are obtained by means of collision experiments and complementary thermochemical considerations. It is shown that upon change of the halide ligand, the weakly solvated ions respond differentially to the increasing need for stabilization of the partial charge on the metal center. For example, whereas F 2 Fe(CH 3 OH) n + ions tend to lose mainly HF for n = 1–3, the loss of HBr is not observed at all for Br 2 Fe(CH 3 OH) n + . Instead, the iron‐bromide cations undergo reductive loss of atomic bromine. Cl 2 Fe(CH 3 OH) n + bears an intermediate position in that both reduction as well as elimination of HCl can occur. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)