Ultraviolet photoelectron spectra of some transition-metal diethyldithiocarbamates

Abstract

He(I) photoelectron spectra of the diethyldithiocarbamates of Cr^III, Fe^III, Co^III, Ni^II, Cu^II, and Zn^II are reported, and a tentative assignment is proposed. ‘d’-Orbital ionization is observed as early and distinct bands for the complexes of Cr, Co, and Ni, while the bands in the 7.5–9.5 eV region, present in all the complexes and related to the known spectrum of NMe₂·CS·SMe, probably arise from the following sequence of molecular orbitals of the chelate rings, π₃ > σ_M–S(n_–) > π₂ > σ_M–S(n₊), mainly derived from sulphur 3p atomic orbitals.