Graphite anion

Cation- and anion-graphite intercalation compounds can be prepared by electrochemical reduction or oxidation of graphite in appropriate electrolytes. Such electrochemical solid-state reactions require mixed conductivity of the solid, i.e., existence of electronic and ionic conductivity. 

With appropriately substituted oxetanes, aluminum-based initiators (321) impose a degree of microstmctural control on the substituted polyoxetane stmcture that is not obtainable with a pure cationic system. A polymer having largely the stmcture of poly(3-hydroxyoxetane) has been obtained from an anionic rearrangement polymerisation of glycidol or its trimethylsilyl ether, both oxirane monomers (322). Polymerisation-induced epitaxy can produce ultrathin films of highly oriented POX molecules on, for instance, graphite (323). Theoretical studies on the cationic polymerisation mechanism of oxetanes have been made (324—326). 

The reaction with 4-nitrophenol and pentafluorophenol in the presence of KF-18-crown-6 has been investigated. Pentafluorophenoxide anion was found to be a better leaving group [82JFC(20)439]. Alkali metal fluorides on graphite can act as catalysts for nucleophilic substitution of pentafluor-opyridine [90JFC(46)57]. 

A particular case of a [3C+2S] cycloaddition is that described by Sierra et al. related to the tail-to-tail dimerisation of alkynylcarbenes by reaction of these complexes with C8K (potassium graphite) at low temperature and further acid hydrolysis [69] (Scheme 24). In fact, this process should be considered as a [3C+2C] cycloaddition as two molecules of the carbene complex are involved in the reaction. Remarkable features of this reaction are (i) the formation of radical anion complexes by one-electron transfer from the potassium to the carbene complex, (ii) the tail-to-tail dimerisation to form a biscarbene anion intermediate and finally (iii) the protonation with a strong acid to produce the... 

Graphite bisulfates are formed by heating graphite with a mixture of sulfuric and nitric acids. In the reaction, the graphite planes are partially oxidized. There is approximately one positive charge for every 24 carbon atoms, and the HS04 anions are distributed between the planes, (a) What effect is this oxidation likely to have on the electrical conductivity (b) What effect would you expect it to have on the x-ray diffraction pattern observed for this material Refer to Major Technique 3 on x-ray diffraction, which follows this set of exercises. 

First reported by Fredenhagen in 1926 F3, F4), the graphite-alkali-metal compounds possess a relative simplicity with respect to other intercalation compounds. To the physicist, their uncomplicated structure and well defined stoichiometry permit reasonable band-structure calculations to be made S2,12) to the chemist, their identity as solid, "infinite radical-anions frequently allows their useful chemical substitution for such homogeneous, molecular-basis reductants as alkali metal-amines and aromatic radical anions N2, B5). 

A number of synthetic procedures are available (Ai2). (2) For precisely defined stoichiometries, the isobaric, two-bulb method of Herold is preferred H5, H6, H2). (2) To generate compounds suitable for organic synthesis work, graphite and alkali metal may be directly combined, and heated under inert gas (Pl, lA). (5) Electrolysis of fused melts has been reported to be effective iN2). 4) Although alkali metal -amine solutions will react with graphite, solvent molecules co-inter-calate with the alkali metal. Utilization of alkali metal-aromatic radical anion solutions suffers the same problem. 

HEAVY ALKYNE ANION RADICALS The Only example of Compounds of this type, the anion radical of the valence isomer of distannyne 51-K, was recently synthesized by Power by the reduction of chlorostannylene 52 with potassium graphite in THF (Scheme 2.39). ... 

The story of the heavy analogs of 6jt-electron cyclopentadienyl anions has culminated in the latest synthesis of a compound containing three heavier group 14 elements (two Si and one Ge) in the ring. This aifionic species 69 Li+ was prepared by the reduction of the disilagermacyclopentadiene precursor 70 with potassium graphite KCg followed by the exchange of countercation from K+ to Li+ by treatment with LiBr (Scheme 2.66). ... 

The electrochemical intercalation of HS04 anions together with H2S04 was described by Thiele in 1934. The composition of the product of prolonged anodic oxidation of graphite in concentrated sulphuric acid is... 

It is very likely that PF6 occupies the Van de Waals gap between the SWNTs in a similar way than in graphite intercalation compounds [6] and in anion-doped fullerenes [7]. Because of lower surface area between... 

The intercalant layer, which comprises the anions A and ligands S, is placed between two positively charged graphite layers. 

Kuroda et al. [505] determined traces of molybdenum in seawater by combined anion exchange and graphite-furnace atomic absorption spectrometry. 

Trace amounts of molybdenum were concentrated from acidified seawater on a strongly basic anion exchange resin (Bio-Rad AG1 X-8 in the chloride form) by treating the water with sodium azide. Molybdenum (VI) complexes with azide were stripped from the resin by elution with ammonium chlo-ride/ammonium hydroxide solution (2 M/2 M). Relative standard deviations of better than 8% at levels of 10 xg per litre were attained for seawater using graphite furnace atomic absorption spectrometry. 

---