Fluoride anion binding by cyclic boronic esters: influence of backbone chelate on receptor integrity


Bresner, Christopher, Day, Joanna K., Coombs, Natalie D., Fallis, Ian A., Aldridge, Simon, Coles, Simon J. and Hursthouse, Michael B. (2006) Fluoride anion binding by cyclic boronic esters: influence of backbone chelate on receptor integrity. Dalton Transactions, (30), 3660-3667. (doi:10.1039/b605031j).

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Original Publication URL: http://dx.doi.org/10.1039/b605031j

Description/Abstract

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).

Item Type: Article
ISSNs: 1477-9226 (print)
Related URLs:
Keywords: bifunctional perfluoroaryl boranes, site olefin polymerization, chemical warfare agents, lewis-acid cocatalysts, x-ray, coordination chemistry, hydride sponge, ion sensor, recognition, ferrocene
Subjects: U Military Science > U Military Science (General)
Q Science > QD Chemistry
Divisions: University Structure - Pre August 2011 > School of Chemistry
ePrint ID: 44392
Date Deposited: 01 Mar 2007
Last Modified: 27 Mar 2014 18:28
URI: http://eprints.soton.ac.uk/id/eprint/44392

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