Manganese(II) tri-tert-butoxysilanethiolate complexes with imidazole-based coligands: A neutral complex with four independent ligands and MNOS2 core (M = Mn) related to the liver alcohol dehydrogenase catalytic center (M = Zn)

The reaction of [Mn{SSi(OBut)3}2(MeOH)4][Mn{SSi(OBut)3}2(MeOH)4] with imidazole and its two methyl substituted derivatives leads to different types of heteroleptic manganese(II) thiolate complexes. Reaction with 1-methylimidazole gives the silanethiolate devoid of methanol but with two nitrogen ligands and thus central MnN2S2 core. The reaction with imidazole leads to the methanol solvated complex with only one nitrogen ligand but manganese coordination sphere enlarged to MnO2NS2 due to an O, S-chelation by tri-tert-butoxysilanethiolate ligand. Molecules of this compound interact through a set of N–H⋯(Me)O–H⋯S hydrogen bonds with methanol hydroxyl group being simultaneously acceptor and donor. With 2-methylimidazole the product is an assembly of two different neutral complexes joined again by hydrogen bonds, however, this time of N–H⋯S type. One of these complexes has the previously mentioned MnO2NS2 core. The second neutral complex exhibits four donor atoms (MnNOS2core) derived from four independent ligands, i.e., two silanethiolate rests, one N-heterocyclic base and one alcohol. This structure presents similarities with a zinc-based alcohol dehydrogenase active site that have never been obtained before, including with other metals (Zn, Co). It may, therefore, be considered the first neutral structural model of liver alcohol dehydrogenase (LADH).