Author(s) Wei, R.; Chen, X.; Gong, Y.
Journal J Phys Chem A
Date Published 2019 Nov 07

Transition metal-SO complexes with different S-O bond lengths serve as ideal models for the understanding of catalytic activation of SO at different stages. Herein, sulfur dioxide complexes of zirconium and hafnium difluorides [MF(OS)] with highly activated S-O bonds were prepared in cryogenic matrixes. The structures of these complexes were identified by infrared spectroscopy and density functional theory calculations. Both ZrF(OS) and HfF(OS) were predicted to have singlet ground states and nonplanar geometries with the metal center coordinated by both oxygens of SO. The much lower O-S-O stretching vibrational frequencies (650-730 cm) in the ligated complexes indicate that the SO ligand should be considered as a singlet SO, which is consistent with the rather long S-O bond lengths (∼1.7 Å) as a result of the two-electron transfer from the metal center to the 1π* orbital of SO upon formation of the complexes.

DOI 10.1021/acs.jpca.9b08744
ISSN 1520-5215
Citation J Phys Chem A. 2019;123(44):95679572.

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