Synthesis, structure and unique reactivity of the ethylzinc derivative of a bicyclic guanidine.

ABSTRACT

An equimolar reaction between ZnEt(2) and 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine (hppH) results in the formation of EtZn(hpp) (1) which crystallizes as a trinuclear agglomerate with the guanidinate ligands spanning 4-coordinate Zn centers. Exposure of a pre-formed THF solution of 1 to undried air leads to a ZnO-incorporating derivative 1(4)·ZnO, while an analogous experiment with CH(2)Cl(2) as solvent leads to a novel tetranuclear mixed aggregate formulated as [EtOZn(hpp)](2)[ClZn(hpp)](2) (2). The composition of 2 indicates that its formation proceeds via a complex multi-step reaction route that involves not only the oxygenation of ZnEt moieties, but also the activation of CH(2)Cl(2), causing the transfer of a chloride anion to the Zn center. Compounds were characterized by (1)H NMR spectroscopy and single-crystal X-ray diffraction analysis.