Matrix infrared spectroscopic and theoretical study on the Pt(SF4) and PtF2SF2 complexes with multiple Pt-S bonding
Qingxiu He1,2, Xiuting Chen1, Yu Gong1
1State Key Laboratory of Thorium Energy, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800, China. gongyu@sinap.ac.cn.
None:
The reactions of laser-ablated platinum atoms with SF4 in neon at 4 K resulted in the formation of two complexes, Pt(SF4) and PtF2SF2. Their structures were identified by the specific infrared absorptions as well as isotopic frequency shifts upon 34S substitution and density functional theory calculations. The Pt(SF4) complex was formed during sample annealing, and was converted to PtF2SF2 upon λ > 280 nm irradiation. Density functional theory calculations at the PBE0 level of theory show that both the PtF2SF2 and Pt(SF4) complexes possess singlet ground states. The former possesses a nonplanar Cs symmetry, whereas a geometry with Pt atop SF4 is obtained for the latter. Geometric and bonding analysis reveal the presence of multiple bonding characters between Pt and S in both the PtF2SF2 and Pt(SF4) complexes, but the PtF2SF2 complex exhibits a less polarized S-based σ bond and more polarized Pt-based π bond than Pt(SF4).
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