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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Fluoride anion binding by cyclic boronic esters: influence of backbone chelate on receptor integrity
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Fluoride anion binding by cyclic boronic esters: influence of backbone chelate on receptor integrity

机译：环状硼酸酯与氟阴离子的结合：主链螯合物对受体完整性的影响

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摘要

A systematic investigation of fluoride anion binding properties as a function of chelate backbone has been carried out for ferrocene functionalised boronic esters of the types FcB(OR)(2) and fc[B(OR)(2)](2) [Fc = ferrocenyl = (eta(5)-C5H5) Fe(eta(5)-C5H4); fc = ferrocendiyl = Fe(eta(5)-C5H4)(2)]. Cyclic boronic esters containing a saturated five- or six-membered chelate ring are readily synthesized from ferrocene, and selectively bind fluoride via Lewis acid/base chemistry in chloroform solution. The resulting complexes are characterized by relatively weak fluoride binding ( e. g. K = 35.8 +/- 9.8 M-1 for FcBO(2)C(2)H(2)Ph(2)- S, S), and by cathodic shifts in the ferrocene oxidation potential that form the basis for electrochemical or colorimetric fluoride detection. The fluoride selectivity of these systems is attributed to relatively weak Lewis acidity, resulting in weak F- binding, and essentially no binding of potentially competitive anions. By contrast, more elaborate Lewis acid frameworks based on calix[4] arene (calixH(4)), such as (FcB)(2)calix or fcB(2)calix, do not survive intact exposure to standard fluoride sources (e.g. [(Bu4N)-Bu-n] F center dot xH(2)O solutions in chloroform or acetonitrile). Instead B - O bond cleavage occurs yielding the parent calixarene; the differences between alkoxo- and aryloxo-functionalised derivatives can be rationalised, at least in part, by consideration of the differences in electron donating capabilities of RO( R = alkyl, aryl).
机译：对于类型为FcB（OR）（2）和fc [B（OR）（2）]（2）的二茂铁官能化硼酸酯的氟化物阴离子结合特性随螯合主链的功能进行了系统研究。二茂铁基=（eta（5）-C5H5）Fe（eta（5）-C5H4）; fc ＝二茂铁基＝ Fe（eta（5）-C5H4）（2）]。含饱和五元或六元螯合环的环状硼酸酯很容易从二茂铁合成，并通过氯仿溶液中的路易斯酸/碱化学选择性地结合氟化物。生成的复合物的特征是相对弱的氟化物结合（例如，FcBO（2）C（2）H（2）Ph（2）-S，S的K = 35.8 +/- 9.8 M-1）和阴极移位二茂铁的氧化电位构成了电化学或比色氟化物检测的基础。这些系统的氟化物选择性归因于相对弱的路易斯酸度，导致弱的F结合，并且基本上没有潜在竞争性阴离子的结合。相比之下，更复杂的基于杯[4]芳烃（calixH（4））的路易斯酸骨架，例如（FcB）（2）calix或fcB（2）calix，在暴露于标准氟化物源的情况下不能幸免（例如[ （Bu4N）-Bu-n] F中心点xH（2）O在氯仿或乙腈中的溶液）。取而代之的是发生B-O键断裂，生成母体杯芳烃;可以至少部分地通过考虑RO（R ＝烷基，芳基）的给电子能力的差异来合理化烷氧基-和芳氧基-官能化衍生物之间的差异。

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