Mononuclear Rare-Earth Metalloligands Exploiting a Divergent Ligand

Rare-earth tris-diketonato [RE(dike)(3)pyterpy] metalloligands can be prepared reacting at room temperature [RE(dike)(3)dme] (dme = 1,2-dimethoxyethane; dike = tta with Htta = 2-thenoyltrifluoroacetone and RE = La, 1; Y, 2; Eu, 3; Dy, 4; or dike = hfac with Hhfac hexafluoroacetylacetone, and RE = Eu, 5; Tb, 6; Yb 7) with 4 '-(4 & tprime;-pyridil)-2,2 ':6 ',2 ''-terpyridine (pyterpy). The molecular structures of 1, 5, 6, and 7 have been studied through single-crystal X-ray diffraction showing mononuclear neutral complexes with the rare-earth ion in coordination number nine and with a muffin-like coordination geometry. [RE(tta)(3)pyterpy] promptly reacts with [M(tta)(2)dme] with formation of [Mpyterpy(2)][RE(tta)(4)](2) (M = Zn, RE = Y, 8; M = Co, RE = Dy, 9). Consistently, [Zn(hfac)(2)dme] reacts at room temperature with 2 equiv of pyterpy yielding [Znpyterpy(2)][hfac](2) 10 that easily can be transformed by reaction with 2 equiv of [Eu(hfac)(3)] in [Znpyterpy(2)][Eu(hfac)(4)](2) 11 that has been structurally characterized. Finally, 1, 2, 3, 5, and 7 metalloligands react at room temperature in few minutes with [PtCl(mu-Cl)PPh3](2) yielding the heterometallic molecular complexes [RE(dike)(3)pyterpyPtCl(2)PPh(3)] (dike = tta, RE = La, 12; Y, 13; Eu; 14; dike = hfac, RE = Eu, 15; Yb, 16).