Ruthenium-thiobase complexes: Synthesis, spectroscopy, density functional studies for trans,cis,cis-[RuII(AsPh3)2 (N,S-2-Thiopyrimidinato)2] and structural analysis of selected weak C–H⋯N and C–H⋯S interactions

Bernhard Lippert has contributed significantly to the understanding of metallamacrocyclic complexes with low valent, late transition metals. In particular, he has pioneered the preparation of metallacalixarenes such as 12-MC-3 and 16-MC-4 structure types. In this article, we provide the preparation of a new 16-MC-4, [Mn4Br4(B(tBuM)PZG)4] [Mn(HOCO2)2], complex made with the ligand potassium N,N-bis(3-methyl-5-tert-butylpyrazolylmethyl)glycinate (KB(tBuM)PZG). In addition to being the first 16-MC-4 that is composed of manganese, this complex is the first example of a transition metal [Mn(II)] being captured in the interior cavity of the 16-MC-4. We discuss how our ligand design leads to the isolated structure due to the steric bulk that has been appended to the pyrazole ligand.