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Kornowicz, A.
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article
Synthesis, Structure and Unique Reactivity of the Ethylzinc Derivative of a Bicyclic Guanidine
Abstract
Equimolar reaction between ZnEt2 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 ZnO-incorporating derivative 14•ZnO, while an analogous experiment with CH2Cl2 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 CH2Cl2, causing the transfer of a chloride anion to the Zn center. Compounds were characterized by 1H NMR spectroscopy and single-crystal X-ray diffraction analysis.