Direct Reactions of Iodine‐Activated Rare‐Earth Metals with Phenols of Varying Steric Bulk

Sonication of rare‐earth metals activated by iodine with 2,6‐di‐ tert ‐butyl‐4‐methylphenol (HOdbmp), 2,6‐diphenylphenol (HOdpp) and mesitol (HOmes) in acetonitrile or tetrahydrofuran (thf) yielded [La(Odbmp) 3 (NCMe) 2 ], [Eu(Odbmp) 2 (thf) 3 ], [Ln(Odpp) 3 (thf) 2 ] (Ln = La, Nd), [Eu(Odpp) 2 (dme) 2 ] (after workup with 1,2‐dimethoxyethane), [Ln 2 (Omes) 6 (thf) 4 ] (Ln = La, Nd), [Y(Omes) 3 (thf) 3 ] and [Eu 3 (Omes) 6 (thf) 6 ] in reactions controlled both by the bulk of the phenol and of the metal. It was noteworthy that Eu II complexes were obtained under the conditions used. The method offers a general, environmentally friendly, metal‐based route to rare‐earth phenolates with prospects for wide application. Some comparison reactions of Ln metals with Hg(C 6 F 5 ) 2 and the phenols were also carried out and the additional complex [Eu(Odpp) 3 (dme)] was isolated. Structures of the new low‐coordinate complexes [La(Odbmp) 3 (NCMe) 2 ] · 2MeCN, [Eu(Odpp) 2 (dme) 2 ] and [Eu(Odpp) 3 (dme)], and a new polymorph of [Eu(Odbmp) 2 (thf) 3 ] · thf, were determined.