Schiff bases derived from pyridyl- or salicyl-aldehydes and aminoalcohols can evolve to heterocyclic oxazolidines, which in the presence of cations allow the formation of uncommon coordination compounds. In this work, we report new NiII and mixed valence MnII/ MnIV complexes derived from pyridyl oxazolidines and the unprecedented characterization of enantiomerically pure oxazolidines derived from the condensation of o-vanillin with phenylglycinol in the presence of NiII cations. The different reactivity of the pyridinic or phenolic Schiff bases has been compared, and the new systems have been structurally, optically, and magnetically characterized