Mononuclear Rare-Earth Metalloligands Exploiting a Divergent Ligand.

Rare-earth tris-diketonato [RE(dike)pyterpy] metalloligands can be prepared reacting at room temperature [RE(dike)dme] (dme = 1,2-dimethoxyethane; dike = tta with Htta = 2-thenoyltrifluoroacetone and RE = La, ; Y, ; Eu, ; Dy, ; or dike = hfac with Hhfac hexafluoroacetylacetone, and RE = Eu, ; Tb, ; Yb ) with 4'-(4‴-pyridil)-2,2':6',2″-terpyridine (pyterpy). The molecular structures of , , , and 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)pyterpy] promptly reacts with [M(tta)dme] with formation of [Mpyterpy][RE(tta)] (M = Zn, RE = Y, ; M = Co, RE = Dy, ). Consistently, [Zn(hfac)dme] reacts at room temperature with 2 equiv of pyterpy yielding [Znpyterpy][hfac] that easily can be transformed by reaction with 2 equiv of [Eu(hfac)] in [Znpyterpy][Eu(hfac)] that has been structurally characterized. Finally, , , , , and metalloligands react at room temperature in few minutes with [PtCl(μ-Cl)PPh] yielding the heterometallic molecular complexes [RE(dike)pyterpyPtClPPh] (dike = tta, RE = La, ; Y, ; Eu; ; dike = hfac, RE = Eu, ; Yb, ).