Alkali-Metal-Ion-Centered Sandwich Structures of 4-Bromophenyl[tris(pentafluorophenyl)]borates and Their Synthetic Utility,Organometallics

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Alkali-Metal-Ion-Centered Sandwich Structures of 4-Bromophenyl[tris(pentafluorophenyl)]borates and Their Synthetic Utility
Organometallics ( IF 2.5 ) Pub Date : 2021-01-19 , DOI: 10.1021/acs.organomet.0c00711
Kento Iwai ₁ , Yoshiyuki Mizuhata _{1,

2} , Norihiro Tokitoh _{1,

2}

Affiliation

Fluorinated tetraarylborates (FTABs) are known as one of the best partners of reactive cations and radical cations. In addition, fascinating effects of ionic substituents have recently gathered much attention from organic chemists. In view of these backgrounds, we newly designed alkali-metal 4-bromophenyl[tris(pentafluorophenyl)]borates 1[M·L] (M = Li, Na, K, Cs, MgBr; L = coordinating solvents) as synthetic units to explore reactive cations as zwitterionic compounds. Through this work, unique alkali-metal-centered sandwich structures of 1[M·L] were revealed by X-ray crystallographic analysis. It should be noted that these are the first examples of the sandwich structure of alkali-metal borates. Their sandwich structures were induced by the M–F_ortho coordination and the cation−π interaction of the p-phenylene moiety, which constructed a cation-capturing pocket. As a synthetic utility of 1[K·C₆H₆], we have demonstrated that the lithium–bromine exchange reaction of 1 afforded the corresponding dianionic species 2, which can be converted to boranuidyltriphenylmethanol 3[K·DME] (DME = 1,2-dimethoxyethane) by the successive addition of benzophenone.

中文翻译：

4-溴苯基[三（五氟苯基）]硼酸酯的碱金属离子居中夹心结构及其合成效用

氟化四芳基硼酸酯（FTAB）是反应性阳离子和自由基阳离子的最佳配偶之一。此外，离子取代基的引人入胜的作用最近引起了有机化学家的广泛关注。鉴于这些背景，我们新设计了碱金属4-溴苯基[三（五氟苯基）]硼酸盐1 [M·L]（M = Li，Na，K，Cs，MgBr； L =配位溶剂）作为合成单元，探索作为两性离子化合物的反应性阳离子。通过这项工作，通过X射线晶体学分析揭示了独特的1 [M·L ]以碱金属为中心的夹心结构。应该注意的是，这些是碱金属硼酸盐的夹心结构的第一个例子。它们的夹心结构是由_MF正交结构引起的对-亚苯基的配位和阳离子-π相互作用，构成了阳离子捕获袋。作为合成效用1 [K·C ₆ H ^ ₆ ]中，我们已经证明，的锂-溴交换反应1，得到相应的双阴离子物种2，其可以被转化为boranuidyltriphenylmethanol 3 [ K·DME ]（DME = 1 （2-二甲氧基乙烷）通过连续加入二苯甲酮而得到。

更新日期：2021-03-08

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