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Title: Ferrocene based Lewis acids for anion sensing
Author: Broomsgrove, Alexander Edward John
Awarding Body: University of Oxford
Current Institution: University of Oxford
Date of Award: 2010
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The synthesis, characterisation and anion binding properties of a series of mono- and bifunctional Lewis acidic borylferrocene compounds are described within this thesis. The original parent compound FcBMes₂ (3.1), revealed a versatile route for the synthesis of such borylferrocenes and subsequently the analogous compound Fc*BMes₂ (3.2) was synthesised. The anion binding properties of (3.1) and (3.2) were investigated and both were shown to bind one equivalent of cyanide. The binding event was signalled by an electrochemical shift (ca. -560 mV) and a quenching of bands at 510 or 542 nm respectively in the UV/Vis spectrum, while the mode of anion binding in the solid state was established by X-ray crystallography for [nBu₄N]⁺[(3.1)·CN]⁻. Incorporation of a suitable redox active dye (i.e. tetrazolium violet for 3.2) allowed conversion of the electrochemical response to a colorimetric change on cyanide binding. However, a competing response for fluoride is also seen for (3.1) and (3.2). Thus a two component system is reported involving (3.2) and the boronic ester FcB(OR)₂ (3.4), [where (OR)₂ = OCH(Ph)CH(Ph)O], which from previous research is known to selectively bind fluoride, and allows for selective colorimetric cyanide sensing by simple Boolean AND/NOT logic. 1,4-C₆H₄(BMes₂)[B(OR)₂] (3.5), 4,4-C12H₈(BMes₂)[B(OR)₂] (3.6) and 1,1′-fc(BMes2)(B(OR)2) (3.7) were synthesised as possible single molecules for discrimination between cyanide and fluoride. (3.5) and (3.6) proved only capable of binding one equivalent of either anion, (3.7) showed some ability to bind two equivalents of fluoride however based on ESI-MS studies although only in the presence of a large excess of anion. Systematic variation of the para-boryl substituent was investigated by synthesis of compounds FcB(XylF)₂ (4.1), FcB(Xyl)₂ (4.2) and FcB(XylOMe)₂ (4.3). Anion binding studies reveal a linear increase in fluoride binding affinity consistent with that expected based on the para,/em>-Hammett parameters, however with only minor differences, while no pattern is observed with respect to their cyanide binding capabilities. The addition of neutral and cationic peripheral substituents has been investigated through synthesis of [1,2-fc(CH₂NMe₂)BMes₂] (4.6) and [1,2-fc(CH₂NMe₃)BMes₂]⁺ (4.7). Subsequent binding studies revealed (4.6) to be moisture sensitive, however reaction of (4.7) with fluoride and cyanide led to formation of the adducts [(4.7)·F]⁻ and [(4.7)·CN]⁻. The anion affinity of (4.7) exhibits a substantial increase when compared to the parent compound (3.1). Even when compared to the isomeric 1,1′ system an increase of approximately three orders of magnitude is seen attributed to the closer nature of the cationic charge and in the fluoride adduct the presence of a cooperative intramolecular hydrogen bond. The 1,1′-bifunctional analogues of the mono-substituted systems were synthesised [e.g. 1,2-fc(BMes₂)₂ (5.1)] and shown to complex two equivalents of fluoride or cyanide in acetonitrile. The 1:1 cyanide adduct of (5.1) was isolated in chloroform however, no evidence for chelation was observed. The analogous systems 1,2-fc(BMes₂)₂ (5.5), 1,2-fc(BXyl₂)2 (5.7), and 1,2-fc(BMes₂)(BXyl₂) (5.8) were also investigated. Reaction of (5.5) with fluoride and cyanide revealed it to bind only one equivalent of either anion, neither however was bound in a chelating fashion although X-ray crystallography revealed cyanide binds exo whilst fluoride binds endo to the B···B cavity. Finally the kinetics of fluoride binding were studied by UV/Vis spectroscopy and showed a systematic increase in rate constant upon reduction of steric bulk.
Supervisor: Aldridge, Simon Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Inorganic chemistry ; Supramolecular chemistry ; Co-ordination chemistry ; boron ; boryl compounds ; cyanides ; ferrocene ; fluorides ; Lewis acids ; sensors