Base fluoride ion

Alternatively, within the Lewis formalism, acids are fluoride-ion acceptors. The prime examples are AsF- and SbFs (which give MF ) and to a lesser extent BF3 which yields BF4 ". A greater diversity is found amongst Lewis bases (fluoride-ion donors), typical examples being XeFg, SF4, CIF3 and BrF3 ... 

Lewis acid (fluoride-ion acceptor) behaviour is exemplified by reactions with NOF and MF to give [N0]+[C1F2] and M+[C1F2] respectively (M = alkali metal or NH4). Lewis base (fluoride ion donor) activity includes reactions with BF3 and ASF5 ... 

Aldridge, S., Bresner, C., Fallis, I. A., Coles, S. J., Hursthouse, M. B., Multidentate Lewis acids synthesis, structure and mode of action of a redox-based fluoride ion sensor. Chem. Commun. 2002, 740-741. 

Hardness and softness refer to special stability of hard-hard and soft-soft interactions and should be carefully distinguished from inherent acid or base strength. For example. both OH and F are hard bases yet the basicity of the hydroxide ion is about lO times that of the fluoride ion. Similariy, both S( and EtjP may be considered soft bases however, the latter is 10 times as strong (toward CHjHg ). It is possible for a strong acid or base to displace a weaker one, even though this appears to violate the principle of hard and soft acids and bases. For example, the stronger, softer base, the sulfite ion, can displace the weak, hard base, fluoride ion, from the hard add. the proton, H -... 

This result is explained by the fact that addition of a hard base (fluoride ions) to the chloride melt containing a weaker hard base (chloride ions) favours stabilization of the halide complexes formed by a harder acid (in our case it is Am3+) as compared with a weaker acid (Am2+). This causes the shift of the equilibrium (1.1.39) to the right, and the disproportionation reaction runs. 

Fluorides ia small (1 ppm ia water, 0.1% ia dentifrices) quantities have been shown to provide dramatic reduction ia dental decay. Fluorides also show promise for bone treatment and ia pharmaceuticals (qv) (see also Chemotherapeutics, anticancer Steroids). However, larger quantities of fluorides can lead to dental fluorosis, bone fracture, and even death. The oral LD q for free fluoride ion ia rats appears to be 50 to 100 mg/kg body weight based on LD q values for several fluorides. 

Analytical Procedures. Oxygen difluoride may be determined conveniently by quantitative appHcation of k, nmr, and mass spectroscopy. Purity may also be assessed by vapor pressure measurements. Wet-chemical analyses can be conducted either by digestion with excess NaOH, followed by measurement of the excess base (2) and the fluoride ion (48,49), or by reaction with acidified KI solution, followed by measurement of the Hberated I2 (4). 

Halogen exchange with KF is not successful ia acetic acid (10). Hydrogen bonding of the acid hydrogen with the fluoride ion was postulated to cause acetate substitution for the haUde however, the products of dissolved KF ia acetic acid are potassium acetate and potassium bifluoride (11). Thus KF acts as a base rather than as a fluorinating agent ia acetic acid. 

Bu4N F , THF, 25°, 1 h, >90% yield. Fluoride ion is very basic especially under anhydrous conditions and thus may cause side reactions with base-sensitive substrates. ArOTBDMS ethers can be cleaved in the presence of alkyl OTBDMS ethers. ... 

It can be cleaved with mild acid, fluoride ion, or base. ... 

Trimethylsilyl ethers are readily cleaved by fluoride ion, mild acids, and bases. If the TMS derivative is somewhat hindered, it also becomes less susceptible to cleavage. A phenolic TMS ether can be cleaved in the presence of an alkyl TMS ether [Dowex lX8(IfO ), EtOH, rt, 6 h, 78% yield]. ... 

It was pointed out earlier that the low nucleophilicity of fluoride ion and its low concentration in HF solutions can create circumstances not commonly observed with the other halogen acids. Under such conditions rearrangement reactions either of a concerted nature or via a true carbonium ion may compete with nucleophilic attack by fluoride ion. To favor the latter the addition of oxygen bases, e.g., tetrahydrofuran, to the medium in the proper concentration can provide the required increase in fluoride ion concentration without harmful reduction in the acidity of the medium. 

In contrast, additions of fluorine and carbon to fluormated olefins are widely investigated The best known processes involve reactions of olefins with fluoride ion to generate carbanionic intermediates [203] that are trapped in situ by carbon-based electrophiles. 

In addition, there is a cleavage reaction whereby a perfluoroorgamc group is cleaved from a metal by a base, for example, phenyllithium [4], ethylmagnesium bromide [5], or a fluoride ion [6] (equations 3-5)... 

This method involves very simple and inexpensive equipment that could be set up m any laboratory [9, 10] The equipment consists of a 250-mL beaker (used as an external half-cell), two platinum foil electrodes, a glass tube with asbestos fiber sealed m the bottom (used as an internal half-cell), a microburet, a stirrer, and a portable potentiometer The asbestos fiber may be substituted with a membrane This method has been used to determine the fluoride ion concentration in many binary and complex fluondes and has been applied to unbuffered solutions from Willard-Winter distillation, to lon-exchange eluant, and to pyrohydrolysis distil lates obtained from oxygen-flask or tube combustions The solution concentrations range from 0 1 to 5 X 10 M This method is based on complexing by fluonde ions of one of the oxidation states of the redox couple, and the potential difference measured is that between the two half-cells Initially, each cell contains the same ratio of cerium(IV) and cerium(tll) ions... 

Aryl and alkyl trimethylsilyl ethers can often be cleaved by refluxing in aqueous methanol, an advantage for acid- or base-sensitive substrates. The ethers are stable to Grignard and Wittig reactions and to reduction with lithium aluminum hydride at —15°. Aryl -butyldimethylsilyl ethers and other sterically more demanding silyl ethers require acid- or fluoride ion-catalyzed hydrolysis for removal. Increased steric bulk also improves their stability to a much harsher set of conditions. An excellent review of the selective deprotection of alkyl silyl ethers and aryl silyl ethers has been published. ... 

Liquid CIF3 can act both as a fluoride ion donor (Lewis base) or fluoride ion acceptor (Lewis acid) to give difluorochloronium compounds and tetrafluorochlorides respectively, e.g. ... 

This last reaction is typical of many in which F3CIO can act as a Lewis base by fluoride ion donation to acceptors such as MF5 (M = P, As, Sb, Bi, V, Nb, Ta, Pt, U), M0F4O, Sip4, BF3, etc. These products are all white, stable, crystalline solids (except the canary yellow PtFe ) and contain the [F2CIO] cation (see Fig. 17.26h) which is isostructural with the isoelectronic F2SO. Chlorine trifluoride oxide can also act as a Lewis acid (fluoride ion acceptor) and is therefore to be considered as amphoteric (p. 225). For example KF, RbF and CsF yield M [F4C10] as white solids whose stabilities increase with increasing size of M+. Vibration spectroscopy establishes the C4 structure of the anion (Fig. 17.29g). 

Acid treatments The principal acid processes were developed in the USA under the name Alodine, and are marketed in the UK as Alocrom and under other names. The original solutions were based on acid solutions containing phosphate, chromate and fluoride ions. Immersion for up to 5 min in the cold or warm solution leads to the deposition of a greenish film containing the phosphates of chromium and aluminium, and possibly some hexavalent chromate. The more recent Alocrom 1 200 process uses an acid solution containing chromate, fluoride and nitrate. Room-temperature immersion for 15 s to 3 min deposits golden-brown coatings which contain chromate as a major constituent. 

Anions. An anion derived from a weak add is itself a weak base. A typical example is the fluoride ion, F-, which is the conjugate base of the weak acid HF. The reaction of the F- ion with water is... 

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