813448-64-5Relevant articles and documents
The structural characteristics of organozinc complexes incorporating N,N'-bidentate ligands
Birch, Samuel J.,Boss, Sally R.,Cole, Sarah C.,Coles, Martyn P.,Haigh, Robert,Hitchcock, Peter B.,Wheatley, Andrew E. H.
, p. 3568 - 3574 (2007/10/03)
Dimethylzinc reacts with an excess of N-2-pyridylaniline 6 to give the homoleptic species, Zn[PhN(2-C5H4N)]2 8. Single crystal X-ray diffraction reveals a solid-state dimer based on an 8-membered (NCNZn)2 core motif. Zn[CyN(2-C5H4N)]Me (Cy = c-C 6H11) 10, prepared by the combination of ZnMe2 with the corresponding cyclohexyl-substituted pyridylamine, is also dimeric in the solid state but reveals a central (ZnN)2 metallacycle. Employment of (p-Tol)NH(2-C5H4N) (p-To = 4-MeC6H 4) 11 yielded the tris(zinc) adduct Zn3[(p-Tol)N(2C 5H4N)]4Me2 12, which incorporates a central chiral molecule of Zn[(p-Tol)N(2-C5H4N)] 2' 12a, that bridges two Zn[(p-Tol)N(2-C5H 4N)]Me' 12b units. A similar trimetallic structure is noted when the pyridylaniline substrate 11 is replaced with the bicyclic guanidine 1,3,4,6,7,8-hexahydro-2h-pyrimido[1,2-a]pyrimidine (hppH), affording Zn 3(hpp)4Me2 13. Spectroscopic studies point to retention of the solid-state structure of 13 in hydrocarbon solution. Reaction of 13 with dimesityl borinic acid, Mes2BOH (Mes = mesityl), affords Zn3(hpp)4(OBMes2)2 14 in which the trimetallic core is retained. This reactivity is in contrast to the closely related reaction of dimeric Zn[Me2NC{N'Pr}2]Me 15 with Mes2BOH, which yielded Zn[Me2NC{N'Pr}2] [OBMes2]'Me2NC{N'Pr} {NH'Pr} 16 as a result of protonation at the guanidine ligand in addition to the Zn-Me bond.