The structural characteristics of organozinc complexes incorporating N,N′-bidentate ligands

摘要: Dimethylzinc reacts with an excess of N-2-pyridylaniline 6 to give the homoleptic species, Zn[PhN(2-C5H4N)]28. Single crystal X-ray diffraction reveals a solid-state dimer based on 8-membered (NCNZn)2 core motif. Zn[CyN(2-C5H4N)]Me (Cy = c-C6H11) 10, prepared by combination ZnMe2 corresponding cyclohexyl-substituted pyridylamine, is also dimeric in solid state but central (ZnN)2 metallacycle. Employment (p-Tol)NH(2-C5H4N) (p-Tol = 4-MeC6H4) 11 yielded tris(zinc) adduct Zn3[(p-Tol)N(2-C5H4N)]4Me212, which incorporates chiral molecule ‘Zn[(p-Tol)N(2-C5H4N)]2’ 12a, that bridges two ‘Zn[(p-Tol)N(2-C5H4N)]Me’ 12b units. A similar trimetallic structure noted when pyridylaniline substrate 11 replaced bicyclic guanidine 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine (hppH), affording Zn3(hpp)4Me213. Spectroscopic studies point retention 13 hydrocarbon solution. Reaction dimesityl borinic acid, Mes2BOH (Mes mesityl), affords Zn3(hpp)4(OBMes2)214 retained. This reactivity contrast closely related reaction Zn[Me2NC{NiPr}2]Me 15 Mes2BOH, Zn[Me2NC{NiPr}2][OBMes2]·Me2NC{NiPr}{NHiPr} 16 as result protonation at ligand addition Zn–Me bond.