Transition metal sulfur oxide complexes that feature SO and SO2 coordination are important species in a series of chemical processes such as catalytic oxidation of sulfur oxides. Fundamental studies on the geometric and electronic structures of these complexes help understand their roles in the relevant chemical reactions. Herein, a series of metal sulfur oxide complexes were produced through the reactions of laser-ablated metal atoms with sulfonyl fluoride (SO2F2) in argon and neon matrixes at 4 K. The product structures were identified by their characteristic infrared absorptions, isotopic frequency ratios upon 18O and 34S substitutions and theoretical calculations. Cerium, thorium, group 3 and 4 metal atoms reacted with SO2F2 to form stable MF2(h2-O2S) complexes in which the sulfur dioxide ligand is bonded to the metal center through two oxygen atoms. The SO2 ligand in the group 3 and cerium complexes can be considered as SO2- while that in the group 4 and thorium complexes is better described as SO22- with a weaker S-O bond. For the other first row metals from Fe to Zn, products in the form of MF2(h1-OSO) containing h1-OSO ligand were identified. The reactions of group 5 metal atoms and SO2F2 resulted in the formation of the OMF2(h2-OS) complexes, in which the sulfur monoxide ligand is in a side-on bonded fashion. The diverse structures of the SO and SO2 coordination complexes are related to the different electronic structures of the metal atoms, which provide further insights into the coordination chemistry of the metal sulfur oxide complexes.

Infrared spectroscopic and theoretical studies of the metal sulfur oxide complexes

2019 Spring National Meeting

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