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Neutral, Anionic, and Paramagnetic 1,3,2-Diazaberyllacyles Derived from Reduced 1,4-Diazabutadienes
Organometallics ( IF 2.8 ) Pub Date : 2020-02-25 , DOI: 10.1021/acs.organomet.0c00017
Albert Paparo 1 , Stephen P. Best 2 , K. Yuvaraj 1 , Cameron Jones 1
Affiliation  

A series of neutral, bulky diazabutadienediyl-substituted beryllacycles [Be(DipDAB)(L)] (DipDAB = [(DipNCH)2]2–, Dip = 2,6-diisopropylphenyl; L = OEt2, THF, :C(RNCH)2; R = Me (TMC), Pri (IPriMe)) have been prepared and characterized by multinuclear NMR spectroscopy and X-ray crystallography. The preparation of similar complexes bearing the smaller tert-butyl-substituted diazabutadienediyl ligand ([(ButNCH)2]2–, viz. ButDAB) was attempted but gave rise to complex product mixtures, several components of which were isolated in trace yields. This phase of the study did, however, lead to the preparation of the homoleptic beryllium diradical complex [Be(ButDAB)2], which was characterized by X-ray crystallography and EPR spectroscopy. In efforts to access BeI–BeI-bonded dianions, [(DipDAB)Be–Be(DipDAB)]2–, reductions of [Be(DipDAB)(L)] were pursued, but these instead afforded largely intractable product mixtures. Treating ethereal solutions of [Be(DipDAB)(OEt2)] with lithium alkyls afforded highly reactive, heterocyclic beryllate salts, [Li(OEt2)2,1][Be(DipDAB)R] (R = Me, Bun). Subsequent treatment of [Li(OEt2)][Be(DipDAB)Bun] with either N,N,N′,N′-tetramethylethylenediamine (tmeda) or N,N,N′,N′′,N′′-pentamethyldiethylenetriamine (pmdeta) led to the formation of [Li(tmeda)2][Be(DipDAB)Bun] and [Li(pmdeta)][Be(DipDAB)Bun]. Reactions between two of the heterocyclic beryllate salts and [BeX2(OEt2)2] (X = Br, I) did not lead to clean salt metathesis reactions but gave mixtures of many products, several of which were isolated in very low yields. While the noninnocent nature of the diazabutadienediyl ligands of [Be(DipDAB)(L)], and the [Be(DipDAB)R] anions, hampered explorations of their further reactivity, these heterocycles hold promise as synthons for beryllium coordination chemistry.

中文翻译:

源自还原的1,4-二氮杂丁二烯的​​中性,阴离子和顺磁性的1,3,2-二氮杂丙烯酰胺

一系列中性的,笨重的重氮杂二烯二基取代的铍环[Be(Dip DAB)(L)](Dip DAB = [(DipNCH)2 ] 2–,Dip = 2,6-二异丙基苯基; L = OEt 2,THF,:C (RNCH)2 ; R =我(TMC),镨(IPriMe))已经被制备和表征通过多核NMR光谱和X-射线晶体学。类似的复合物承载较小的制备丁基取代的diazabutadienediyl配体([(卜NCH)2 ] 2-,即尝试了DAB),但产生了复杂的产品混合物,其中一些组分以微量收率分离出来。然而,该研究阶段确实导致了均相铍双自由基配合物[Be(Bu t DAB 2 ]的制备,其特征在于X射线晶体学和EPR光谱学。在尝试使用Be I –Be I键合的二价阴离子[(Dip DAB)Be–Be(Dip DAB)] 2–的过程中,尝试降低[Be(Dip DAB)(L)],但这些替代品在很大程度上难以解决产品混合物。处理[Be(Dip DAB)(OEt 2)的醚溶液)]与烷基锂一起提供高反应性的杂环铍酸盐[Li(OEt 22,1 ] [Be(Dip DAB)R](R = Me,Bu n)。用NNN ',N'-四甲基乙二胺(tmeda)或NNN ',N '',N ''对[Li(OEt 2)] [Be(Dip DAB)Bu n ]进行后续处理-五甲基二亚乙基三胺(pmdeta)导致[Li(tmeda)2 ] [Be(Dip DAB)Bu n的形成]和[Li(pmdeta)] [Be(Dip DAB)Bu n ]。两种杂环铍酸酯盐与[BeX 2(OEt 22 ](X = Br,I)之间的反应未导致纯净的盐复分解反应,但产生了许多产物的混合物,其中许多产物的分离产率非常低。尽管[Be(Dip DAB)(L)]和[Be(Dip DAB)R] -阴离子的二氮杂丁二烯基配体的非纯性质阻碍了对其进一步反应性的探索,但这些杂环有望作为铍配位化学的合成子。
更新日期:2020-02-25
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