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‴-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(μ-Cl)PPh 3 ] 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 ).