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Four new lead(II) thiosaccharinate complexes: [Pb(tsac)2H2O] (1) (tsac: thiosaccharinate anion), [Pb2(tsac)4(py)4] (2) (py: pyridine), [Pb(tsac)(o‐phen)2](tsac)·CH3CN (3) (o‐phen: 1,10‐phenantroline), and [Pb(tsac)2(bipy)] (4) (bipy: 2,2′‐bipyridine) were prepared. The infrared and electronic spectra as well as the thermal analysis of all the compounds were recorded and discussed. The thiosaccharinate anion acts in three different coordination forms, one of then reported for the first time. The crystal structures of complexes 2 and 3 have been determined by single crystal X‐ray diffractometry. In complex 2, two monomeric moieties are joined together forming a symmetric bis‐μ‐sulphur bridged dimer by interaction of two lead(II) atoms through the exocyclic sulphur atoms of two thiosaccharinate ligands. The seven‐fold coordination sphere of each lead atom is completed by two pyridine nitrogen atoms and by another sulfur and two nitrogen atoms of the thiosaccharinate anions. In complex 3, the lead(II) atom is coordinated by four nitrogen atoms of two 1,10‐phenantroline molecules and by the sulfur and nitrogen atoms of one thiosaccharinate ion. The second anion has an electrostatic interaction with the nucleus.

A general alteration pattern of two transitional clay mineral assemblages was determined by petrography and X-ray diffractometry studies at the Tandilia Late Proterozoic unconformity zone, around the Barker locality: (1) K-white mica + chlorite + calcite ± anatase-rutile ± secondary quartz (farther from the unconformity) and (2) pyrophyllite + K-white mica + Ti-rich hematite ± aluminium phosphate-sulphate minerals ± tourmaline ± anatase-rutile (closer to the unconformity). The local occurrence of Na in K-white micas and K-Na in pyrophyllite is described for the first time. Possible interlayering with intermediate K-Na mica and paragonite is indicated by detailed X-ray diffraction analyses. A negative Eu anomaly (Eu/Eu* = 0.24), strongly positive Eu anomaly (Eu/Eu* =11.7) and positive Ce anomaly characterized rapid changes from an unaltered basement to the most altered basement and sedimentary rocks at the unconformity. Aluminium phosphate-sulphate minerals dominate patterns of LREE. A model of hydrothermal alteration comparable to that of unconformity-related uranium deposits is presented.