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Direct Reactions of Iodine‐Activated Rare‐Earth Metals with Phenols of Varying Steric Bulk
Author(s) -
Deacon Glen B.,
Hamidi Shima,
Junk Peter C.,
Kelly Rory P.,
Wang Jun
Publication year - 2014
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201301362
Subject(s) - chemistry , tetrahydrofuran , dimethoxyethane , acetonitrile , steric effects , metal , phenols , inorganic chemistry , iodine , rare earth , phenol , medicinal chemistry , organic chemistry , mineralogy , electrolyte , electrode , solvent
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.