Differing Coordination Environments in Transition Metal Derivatives of 1,8-Bis(silylamido)naphthalene Ligands

Four low-coordinate transition metal amido complexes featuring sterically demanding 1,8-bis(silylamido)naphthalene ligands are reported. Reaction of one molar equivalent of 1,8-C10H6(NLiSiMe3)2 with ZnCl2 yields the structurally authenticated dimer [1,8-C10H6(NSiMe3)2Zn]2 (1), where the 1,8-bis(silylamido)naphthalene moiety is acting as both a chelating and bridging ligand. The effect on the resulting transition metal complexes of increasing the steric demands of the ligand was investigated, using the triisopropylsilyl-substituted ligand 1,8-C10H6(NSiiPr3)2. Reaction of one molar equivalent of 1,8-C10H6(NLiSiiPr3)2 with ZnCl2 or FeCl2(THF)1.5 yields 1,8-C10H6(NSiiPr3)2M(μ-Cl)Li(THF)3 (M = Zn, 2; M = Fe, 3), respectively; the coordination of the ClLi(THF)3 moiety to the metal center in these compounds is a rare structural motif in the coordination chemistry of the d-block elements. Analogous reaction of 1,8-C10H6(NLiSiiPr3)2 with MnCl2 affords the mixed-metal Li−Mn−amido complex 1,8-C10H6(NSiiPr3)2Li(THF)MnCl(THF) (4) which features an unusual LiMnN2 core.