Photosensitive Tin Sulfur Dioxide Complexes with Unexpected Bonding Modes

Abstract

Infrared spectra of the matrix‐isolated Sn(η2‐O2S), Sn(η2‐OSO), Sn(η2‐O2S)(η1‐OSO), Sn(η2‐O2S)2, OSn2(η2‐SO), and Sn(μ2‐O2)SnS molecules were observed following laser‐ablated Sn atom reactions with SO2 during condensation in solid argon. The assignments for the major vibrational modes were confirmed by appropriate S18O2 and 34SO2 isotopic shifts and density functional vibrational frequency calculations (B3LYP and BPW91). Interestingly, the mononuclear complexes are interconvertible; that is, irradiation induces the isomerization of Sn(η2‐O2S) and Sn(η2‐O2S)(η1‐OSO) to Sn(η2‐OSO) and Sn(η2‐O2S)2, respectively, and vice versa on annealing. However, there is no evidence of isomerization reaction in between the binuclear molecules OSn2(η2‐SO) and Sn(μ2‐O2)SnS. Bonding in these products is discussed, and the electronic structure changes associated with different bonding types are revealed, which is crucial for the observed photochemical reactions.

Sulfur Dioxide Complexes of Main-Group Elements: from SO20 to SO2– and SO22– upon Coordination to Aluminum and Silicon Difluorides

“…The absence of Lewis acid–base adducts makes it possible for frustrated Lewis pairs to bind another molecule prior to the activation of a chemical bond. , In addition to the unique reactivities of main-group elements, a great deal of effort has been devoted to the elucidation of the relevant reaction mechanisms as well, − and the structures of complexes formed between main-group elements and small molecules are crucial for a better understanding of the mechanisms regarding small-molecule activation. The complexes of main-group elements and small molecules such as CO, N 2 , C 2 H 2 , and H 2 have been widely studied and summarized, − while less attention has been paid to SO 2 , − the activation and functionalization of which are also important tasks due to the environmental issues arising from SO 2 .…”