Issue 24, 2013

Spontaneous sulfur dioxide activation by Group V metal (V, Nb, Ta) atoms in excess argon at cryogenic temperatures

Abstract

Reactions of laser-ablated V, Nb and Ta atoms with SO2 in excess argon during condensation gave new absorptions in the M[double bond, length as m-dash]O stretching region, which were assigned to metal sulfide oxides SMO2 and anions SMO2 (M = V, Nb, Ta). The metal oxide complex OV(η2-SO) was also identified through the V[double bond, length as m-dash]O and the characteristic side-on coordinated S–O stretching modes. The assignments of major vibrational modes were confirmed by appropriate S18O2 and 34SO2 isotopic shifts, and density functional frequency calculations. DFT calculations were employed to study the behavior of reactions of Group V bare metal atoms with SO2, and a representative profile was derived which not only showed the preferred coordinating fashion of metal atoms but also tracked the path of S–O bond activation. The η2-O,O′ bridge coordinated complexes are preferred with energy decreases of ca. 50 kcal mol−1 for all three metals, which facilitate the activation of two S–O bonds in succession and finally direct the reaction to the most stable molecules SMO2 (M = V, Nb, Ta) along the potential energy surface (PES). Finally the SMO2 molecules capture electrons to give anions SMO2 with about 3.6 eV electron affinities based on DFT calculations.

Graphical abstract: Spontaneous sulfur dioxide activation by Group V metal (V, Nb, Ta) atoms in excess argon at cryogenic temperatures

Article information

Article type
Paper
Submitted
15 Mar 2013
Accepted
19 Apr 2013
First published
22 Apr 2013

Phys. Chem. Chem. Phys., 2013,15, 9823-9832

Spontaneous sulfur dioxide activation by Group V metal (V, Nb, Ta) atoms in excess argon at cryogenic temperatures

X. Liu, X. Wang, Q. Wang and L. Andrews, Phys. Chem. Chem. Phys., 2013, 15, 9823 DOI: 10.1039/C3CP51137E

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