Structural Investigation of New Lithium Amidinates and Guanidinates
Structural Investigation of New Lithium Amidinates and Guanidinates
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DOI：
10.1002/zaac.201800486
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发表时间：
2019-02
期刊：
影响因子：
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通讯作者：
Phil Liebing;Nicole Harmgarth;V. Lorenz;Florian Zörner;L. Hilfert;Sabine Busse;F. Edelmann
中科院分区：
文献类型：
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作者：
Phil Liebing;Nicole Harmgarth;V. Lorenz;Florian Zörner;L. Hilfert;Sabine Busse;F. Edelmann
制备了一系列潜在有用的脒基锂和胍基锂，并对其进行了充分表征。N，N′-二异丙基碳二亚胺与苯基锂在乙醚中反应得到脒基锂[PhC（NiPr）2Li（OEt 2）]2（1）。用仲氨基锂LiNR 2 [R2= Et 2，iPr 2，（CH 2）4]类似地处理N，N′-二有机基马来酰亚胺R ′-N=C=N-R′ [R′ =iPr，环己基（Cy）]，然后从THF或1，4-二氧杂环己烷中结晶，得到胍基锂[R2 NC（NR′）2Li（S）]2[2：R= Et，R′ =iPr，S = THF;3：R2=（CH 2）4，R′ = iPr，S = THF;4：R=R′ =iPr，S = 1/2 1，4-二氧杂环己烷;5：R2=（CH 2）4，R′ = Cy，S = 1，4-二氧杂环己烷]，为结晶固体。N-锂氮丙啶与相应的N-二酰亚胺反应得到溶剂缺乏的[{C2 H4 NC（NiPr 2）2} 2Li 2（THF）]2（6）和[C2 H4 NC（NEt）（NtBu）Li（THF）]2（7）。晶体结构测定揭示了1 -5的常见梯形二聚体结构的存在。化合物6在晶体中以两个梯形二聚体的二聚体形式存在，并且7表现出包含八元C2 N4 Li 2环的不寻常的二聚体结构。
A series of potentially useful lithium amidinates and guanidinates were prepared and fully characterized. Treatment ofN,N′‐diisopropylcarbodiimide with phenyllithium in diethyl ether afforded the lithium amidinate [PhC(NiPr)2Li(OEt2)]2(1). Similar treatment ofN,N′‐diorganocarbodiimidesR′–N=C=N–R′ [R′ =iPr, cyclohexyl (Cy)] with secondary lithium amides LiNR2[R2= Et2,iPr2, (CH2)4] followed by crystallization from THF or 1,4‐dioxane gave the lithium guanidinates [R2NC(NR′)2Li(S)]2[2:R= Et,R′ =iPr, S = THF;3:R2= (CH2)4,R′ =iPr, S = THF;4:R=R′ =iPr, S = ½ 1,4‐dioxane;5:R2= (CH2)4,R′ = Cy, S = 1,4‐dioxane] as crystalline solids. Reaction ofN‐lithioaziridine with the corresponding carbodiimides afforded solvent‐deficient [{C2H4NC(NiPr2)2}2Li2(THF)]2(6), and [C2H4NC(NEt)(NtBu)Li(THF)]2(7). Crystal structure determination revealed the presence of common ladder‐type dimeric structures for1–5. Compound6exists as a dimer of two ladder‐type dimers in the crystal, and7exhibits an unusual dimeric structure comprising an eight‐membered C2N4Li2ring.