Cyclic M(SO2) (M=Zn,Cd) and its Anions: Matrix Infrared Spectra and DFT Calculations

Reaction of laser ablated zinc and cadmium atoms with SO₂ molecules was studied by low temperature matrix isolation infrared spectroscopy. Cyclic M(SO₂) and anion M(SO₂)^- (M=Zn, Cd) were produced in excess argon and neon, which were identified by ³⁴SO₂ and S¹⁸O₂ isotopic substitutions. The observed infrared spectra and molecular structures were confirmed by density functional theoretical calculations. Natural charge distributions indicated significant electron transfer from s orbitals of zinc or cadmium metal atom to SO₂ ligand and cyclic M(SO₂) complexes favored “ion pair” M⁺(SO₂)^- formation, which were trapped in low temperature matrices. In addition Zn-O or Cd-O bond in M(SO₂) exhibited strong polarized covalent character. Reaction of Hg atom with SO₂ was also investigated, but no reaction product was observed, due to the relativistic effect that resulted in the contraction of 6s valence shell and high ionization potential of Hg atom