Synthesis, Structural Characterization, and Reactivity of Mono(amidinate) Rare-Earth-Metal Bis(aminobenzyl) Complexes

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• 作者：Jianquan Hong ; Lixin Zhang ; Kai Wang ; Zhenxia Chen ; Limin Wu ; Xigeng Zhou
• 刊名：Organometallics
• 出版年：2013
• 出版时间：December 23, 2013
• 年：2013
• 卷：32
• 期：24
• 页码：7312-7322
• 全文大小：662K
• ISSN：1520-6041

文摘

Three kinds of solvated lithium amidinates with different coordination models were obtained via recrystallization of [PhC(NC₆H₄ⁱPr₂-2,6)₂]Li(THF) (1a) in different solvents. Treatment of o-Me₂NC₆H₄CH₂Li with LLnCl₂(THF)_n (2; L = [PhC(NC₆H₄ⁱPr₂-2,6)₂]^{鈭?/sup> (NCNdipp), [o-Me₂NC₆H₄CH₂C(NC₆H₄iPr₂-2,6)₂]鈭?/sup> (NCNdipp鈥?) formed in situ from reaction of LnCl₃(THF)_x with LLi(THF) gave the rare-earth-metal bis(aminobenzyl) complexes LLn(CH₂C₆H₄NMe₂-o)₂ (L = NCNdipp, Ln = Sc (3a), Y (3b), Lu (3c); L = NCNdipp鈥? Ln = Sc (3d), Lu (3e)) in high yields. Reactions of complexes 3 with CO₂, PhNCO, 2,6-diisopropylaniline, and S have been explored. CO₂ inserted into each Ln鈥揅 bond of complexes 3a鈥?b>c to form the dual-core complexes [(NCNdipp)Sc(渭-畏1:畏1-O₂CCH₂C₆H₄NMe₂-o)₂]₂ (4a) and [(NCNdipp)Ln(渭-畏1:畏2-O₂CCH₂C₆H₄NMe₂-o)(渭-畏1:畏1-O₂CCH₂C₆H₄NMe₂-o)]₂ (Ln = Y (4b), Lu (4c)). The reaction of 3b,c,e with PhNCO produced LLu[OC(CH₂C₆H₄NMe₂-o)NPh]₂(thf) (L = NCNdipp, Ln = Y (5b), Lu (5c); L = NCNdipp鈥? Ln = Lu (5e)). Protonolysis of 3a,b by 2,6-diisopropylaniline formed straightforwardly the 渭₂-imido complexes [(NCNdipp)Ln(渭-NC₆H₄iPr₂-2,6)]₂ (Ln = Sc (6a), Lu (6c)). Reaction of 3e with S₈ afforded the sulfur insertion products (NCNdipp鈥?Lu(CH₂C₆H₄NMe₂-o)(SCH₂C₆H₄NMe₂-o)(thf) (7e) and (NCNdipp鈥?Lu(SCH₂C₆H₄NMe₂-o)₂(thf)₂ (7f) in high yields, respectively, depending on the stoichiometric ratio. All of these complexes were fully characterized by elemental analysis, NMR spectroscopy, and X-ray structural determinations.}