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Fluorinated antimony(v) derivatives: strong Lewis acidic properties and application to the complexation of formaldehyde in aqueous solutions.

ABSTRACT: As part of our ongoing studies of water tolerant Lewis acids, we have synthesized and investigated the properties of Sb(C₆F₅)₃(O₂C₆Cl₄), a fluorinated stiborane whose Lewis acidity approaches that of B(C₆F₅)₃. While chloroform solutions of this Lewis acid can be kept open to air or exposed to water for extended periods of time, this new Lewis acid reacts with P ^t Bu₃ and paraformaldehyde to form the corresponding formaldehyde adduct ^t Bu₃P-CH₂-O-Sb(C₆F₅)₃(O₂C₆Cl₄). To test if this reactivity can also be observed with systems that combine the phosphine and the stiborane within the same molecule, we have also prepared o-C₆H₄(PPh₂)(SbAr₂(O₂C₆Cl₄)) (Ar = Ph, C₆F₅). These yellow compounds, which possess an intramolecular P?Sb interaction, are remarkably inert to water but do, nonetheless, react with and accomodate formaldehyde into the P/Sb pocket. In the case of the fluorinated derivative o-C₆H₄(PPh₂)(Sb(C₆F₅)₂(O₂C₆Cl₄)), formaldehyde complexation, which occurs in water/dichloromethane biphasic mixtures, is accompanied by a colourimetric turn-off response thus highlighting the potential that this chemistry holds in the domain of molecular sensing.

SUBMITTER: Tofan D

PROVIDER: S-EPMC5363782 | biostudies-literature | 2016 Nov

REPOSITORIES: biostudies-literature

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Fluorinated antimony(v) derivatives: strong Lewis acidic properties and application to the complexation of formaldehyde in aqueous solutions.

Tofan Daniel D Gabbaï François P FP

Chemical science 20160711 11

As part of our ongoing studies of water tolerant Lewis acids, we have synthesized and investigated the properties of Sb(C6F5)3(O2C6Cl4), a fluorinated stiborane whose Lewis acidity approaches that of B(C6F5)3. While chloroform solutions of this Lewis acid can be kept open to air or exposed to water for extended periods of time, this new Lewis acid reacts with P t Bu3 an ...[more]

PMID: 28451122

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Project description:We present the analysis of formaldehyde (HCHO) in anhydrous methanol (CH3OH) as a case study to quantify HCHO in non-aqueous samples. At higher concentrations (C > 0.07 M), we detect a product of HCHO, methoxy methanol (MM, CH3OCH2OH), by Fourier transform infrared spectroscopy, FTIR. Formaldehyde reacts with CH3OH, CD3OH, and CD3OD as shown by FTIR with a characteristic spectral feature around 1,195 cm-1 for CH3OH used for the qualitative detection of MM, a formaldehyde derivative in neat methanol. Ab initio calculations support this assignment. The extinction coefficient for 1,195 cm-1 is in the order of 1.4 × 102 M-1cm-1, which makes the detection limit by FTIR in the order of 0.07 M. For lower concentrations, we performed the quantitative analysis of non-aqueous samples by derivatization with dinitrophenylhydrazine (DNPH). The derivatization uses an aqueous H2SO4 solution to yield the formaldehyde derivatized hydrazone. Ba(OH)2 removes sulfate ions from the derivatized samples and a final extraction with isobutyl acetate to yield a 1:1 methanol: isobutyl acetate solvent for injection for electrospray ionization (ESI). The ESI analysis gave a linear calibration curve for concentrations from 10 to 200 µM with a time-of-flight analyzer (TOF). The detection and quantification limits are 7.8 and 26 μM, respectively, for a linear correlation with R 2 > 0.99. We propose that the formaldehyde in CH3OH is in equilibrium with the MM species, without evidence of HCHO in solution. In the presence of water, the peaks for MM become less resolved, as expected from the well-known equilibria of HCHO that favors the formation of methylene glycol and polymeric species. Our results show that HCHO, in methanol does not exist in the aldehyde form as the main chemical species. Still, HCHO is in equilibrium between the production of MM and the formation of hydrated species in the presence of water. We demonstrate the ESI-MS analysis of HCHO from a non-aqueous TiO2 suspension in methanol. Detection of HCHO after illumination of the colloid indicates that methanol photooxidation yields formaldehyde in equilibrium with the solvent.

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Fluorinated antimony(v) derivatives: strong Lewis acidic properties and application to the complexation of formaldehyde in aqueous solutions.

Publications

Fluorinated antimony(v) derivatives: strong Lewis acidic properties and application to the complexation of formaldehyde in aqueous solutions.

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