Mass spectral fragmentation of metal dithiocarbamate complex salts

A summary of the mass spectra of metal dithiocarbamate complex salts (ML₂ and ML₃) is presented. Only divalent metal dithiocarbamate ions without an electronic configuration containing an inert s-orbital electron pair exhibited both expulsion of a ligand radical (L) and the neutral even electron species (L–H) generated from the ligand via hydrogen transfer to the metal-containing fragment ion. Divalent metal dithiocarbamate ions can be generated either by direct electron impact ionization of gas phase ML₂ molecules or ionization of ML₃ molecules followed by loss of a ligand radical. A highly stable sp² hybridized, gas phase ion of a monobidentate lead dithiocarbamate complex is proposed.