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Synthesis and structural characterization of a series of carboxylic acid modified cerium(III) alkoxides

Boyle, Timothy J.; Tribby, Louis J.; Bunge, Scott D.

A series of cerium alkoxides were synthesized from the reaction of Ce{N[Si(CH3)3]2}3 and the appropriate alcohol: neopentyl alcohol [H-OCH2C(CH3) 3 = H-ONep], tert-butyl alcohol [H-OC(CH3)3 = H-OtBu], o-(tert-butyl)phenol {H-OC6H4[C(CH 3)3]-2 = H-oBP), 2,6-dimethylphenol [H-OC 6H3(CH3)2-2,6 = H-DMP], 2,6-diisopropylphenol {H-OC6H3[CH(CH3) 2]2-2,6 = H-DIP}, 2,6-di-tert-butylphenol {H-OC 6H3[C(CH3)3]2-2,6 = H-DBP}, or 2,6-diphenylphenol [H-OC6H3(C6H 5)2-2,6 = H-DPP] using toluene (tol), tetrahydrofuran (THF) or pyridine (py). The precursors were characterized as [Ce(μ-ONep) 2(ONep)]4 (1), Ce4(μ3-OtBu) 3(μ-OtBu)4(OtBu)5 (2), Ce 3(μ3-OtBu)3(H-OtBu)2(OtBu) 3(H-OtBu)2 (2a), Ce(OBP)3(THF)3 (3), [Ce(μ-DMP)(DMP)2(solv)2]2 [solv = THF (4) and py (4a)], Ce(DIP)3(THF)3 (5), Ce(DPP) 3(THF)2 (6). Once isolated, several of these species were further reacted with a series of sterically varied carboxylic acid modifiers including isobutyric acid [H-O2CCH(CH3)2 = H-OPc] and trimethylacetic acid [H-O2CC(CH3)3 = H-OBc]. The products were isolated as [Ce(OR)(μ-ORc)(μc-ORc) (py)]2 [OR = oBP, OBc: 7; DMP, OPc: 8; DMP, OBc: 9; DIP, OPc: 10]. These compounds were identified by single-crystal X-ray diffraction and powder XRD analyses. Several novel structure types are added to the cerium alkoxide family of compounds. © Wiley-VCH Verlag GmbH & Co. KGaA, 2006.