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

Fluoride anion binding by cyclic boronic esters: influence of backbone chelate on receptor integrity
Fluoride anion binding by cyclic boronic esters: influence of backbone chelate on receptor integrity
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).
bifunctional perfluoroaryl boranes, site olefin polymerization, chemical warfare agents, lewis-acid cocatalysts, x-ray, coordination chemistry, hydride sponge, ion sensor, recognition, ferrocene
1477-9226
3660-3667
Bresner, Christopher
b8ec5197-c224-49a3-a654-e091db75fb52
Day, Joanna K.
46d4e919-f0ad-4b85-8c88-ea5be867c605
Coombs, Natalie D.
248c48b7-8b41-4c98-bb3e-b306c0c37bdf
Fallis, Ian A.
6f14a47a-a4f7-405d-94eb-33fe818a21c5
Aldridge, Simon
de66448a-0f63-4b8b-ac55-f78dcd4830ea
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Bresner, Christopher
b8ec5197-c224-49a3-a654-e091db75fb52
Day, Joanna K.
46d4e919-f0ad-4b85-8c88-ea5be867c605
Coombs, Natalie D.
248c48b7-8b41-4c98-bb3e-b306c0c37bdf
Fallis, Ian A.
6f14a47a-a4f7-405d-94eb-33fe818a21c5
Aldridge, Simon
de66448a-0f63-4b8b-ac55-f78dcd4830ea
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da

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).

Record type: Article

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).

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More information

Published date: 2006
Keywords: bifunctional perfluoroaryl boranes, site olefin polymerization, chemical warfare agents, lewis-acid cocatalysts, x-ray, coordination chemistry, hydride sponge, ion sensor, recognition, ferrocene

Identifiers

Local EPrints ID: 44392
URI: http://eprints.soton.ac.uk/id/eprint/44392
ISSN: 1477-9226
PURE UUID: f304e189-2100-4026-8b78-2aa71f7b5f5b
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

Catalogue record

Date deposited: 01 Mar 2007
Last modified: 19 Nov 2019 01:53

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