Mononuclear Rare-Earth Metalloligands Exploiting a Divergent Ligand

Rare-earth tris-diketonato [RE(dike)3pyterpy] metalloligands can be prepared reacting at room temperature[RE(dike)3dme] (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‴-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 mononuclearneutral complexes with the rare-earth ion in coordination number nine and with a muffin-like coordination geometry.[RE(tta)3pyterpy] promptly reacts with [M(tta)2dme] with formation of [Mpyterpy2][RE(tta)4]2 (M = Zn, RE = Y, 8; M = Co, RE= Dy, 9). Consistently, [Zn(hfac)2dme] reacts at room temperature with 2 equiv of pyterpy yielding [Znpyterpy2][hfac]2 10 thateasily can be transformed by reaction with 2 equiv of [Eu(hfac)3] in [Znpyterpy2][Eu(hfac)4]2 11 that has been structurallycharacterized. Finally, 1, 2, 3, 5, and 7 metalloligands react at room temperature in few minutes with [PtCl(μ-Cl)PPh3]2 yielding theheterometallic molecular complexes [RE(dike)3pyterpyPtCl2PPh3] (dike = tta, RE = La, 12; Y, 13; Eu; 14; dike = hfac, RE = Eu, 15;Yb, 16).