Dimethylzinc reacts with an excess of N-2-pyridylaniline 6to give the homoleptic species, ZnPhN2-C5H4N28. Single crystal X-ray diffraction reveals a solid-state dimer based on an 8-membered NCNZn2core motif. ZnCyN2-C5H4NMe Cy c-C6H1110, prepared by the combination of ZnMe2with the corresponding cyclohexyl-substituted pyridylamine, is also dimeric in the solid state but reveals a central ZnN2metallacycle. Employment of p-TolNH2-C5H4N p-Tol 4-MeC6H411yielded the triszinc adduct Zn3p-TolN2-C5H4N4Me212, which incorporates a central chiral molecule of ‘Znp-TolN2-C5H4N2’ 12a, that bridges two ‘Znp-TolN2-C5H4NMe’ 12bunits. A similar trimetallic structure is noted when the pyridylaniline substrate 11is replaced with the bicyclic guanidine 1,3,4,6,7,8-hexahydro-2H-pyrimido1,2-apyrimidine hppH, affording Zn3hpp4Me213. Spectroscopic studies point to retention of the solid-state structure of 13in hydrocarbon solution. Reaction of 13with dimesityl borinic acid, Mes2BOH Mes mesityl, affords Zn3hpp4OBMes2214in which the trimetallic core is retained. This reactivity is in contrast to the closely related reaction of dimeric ZnMe2NCNiPr2Me 15with Mes2BOH, which yielded ZnMe2NCNiPr2OBMes2·Me2NCNiPrNHiPr 16as a result of protonation at the guanidine ligand in addition to the Zn–Me bond.