Addition of polyhalides

Connection of dendrimers via treatment with multifunctional cross-linking-type reagents such as the addition of polyhalides to amine-terminated dendrimers 78 results in randomly positioned dendritic assemblies. Dendrimers have also been bridged by the incorporation of copolymerizable units into reactions with dendrimers possessing polymerizable, terminal olefins. 79,80 ... 

Azodiisobutyronitrile Addition of polyhalides to carbon-carbon bonds... 

Pure NI3 has not been isolated, but the structure of its well-known extremely shock-sensitive adduct with NH3 has been elucidated — a feat of considerable technical virtuosity.Unlike the volatile, soluble, molecular solid NCI3, the involatile, insoluble compound [Nl3.NH3] has a polymeric structure in which tetrahedral NI4 units are comer-linked into infinite chains of -N-I-N-I- (215 and 230 pm) which in turn are linked into sheets by I-I interactions (336 pm) in the c-direction in addition, one I of each NI4 unit is also loosely attached to an NH3 (253 pm) that projects into the space between the sheets of tetra-hedra. The stmcture resembles that of the linked Si04 units in chain metasilicates (p. 349). A further interesting feature is the presence of linear or almost linear N-I-N groupings which suggest the presence of 3-centre, 4-electron bonds (pp. 63, 64) characteristic of polyhalides and xenon halides (pp. 835-8, 897). 

The synthesis of polyhalide salts, R4NX , used in electrophilic substitution reactions, are described in Chapter 2 and H-bonded complexed salts with the free acid, R4NHX2, which are used for example in acid-catalysed cleavage reactions and in electrophilic addition reactions with alkenes, are often produced in situ [33], although the fluorides are obtained by modification of method I.I.I.B. [19, 34], The in situ formation of such salts can inhibit normal nucleophilic reactions [35, 36]. Quaternary ammonium chlorometallates have been synthesized from quaternary ammonium chlorides and transition metal chlorides, such as IrClj and PtCl4, and are highly efficient catalysts for phase-transfer reactions and for metal complex promoted reactions [37]. 

Although chlorination, bromination and iodination of thiophenes by polyhalide salts require forcing conditions with the addition of zinc chloride [52], halogenation of acridine and acridone has been recorded to yield both 3-halo and 3,7-dihalo derivatives under relatively mild reaction conditions [53], However, whereas chloro-, bromo- and iodo-compounds are readily obtained from acridone, acridine only forms the bromo derivatives, as it produces stable complexes with the dichloroiodate and tetrachloroiodate salts [53]. 

Vinyl halides are so inert that none has been converted to a fluoride by halogen exchange. Vinyl fluorides have been synthesized from saturated polyhalides by dehalogenation with zinc and by dehydrohalo- genation with alcoholic alkali, and from acetylene by addition of one molecule of hydrogen fluoride.12 18... 

The starting polyhalides are obtained in reasonable yield by addition of, eg., 1,1,1-trichloropropane to 2-chloropropene, initiated by Fe(CO)5 — HMPA. Treatment with zinc in DMF leads to good yields of 1,2-dialkylcyclopropenes, but the reaction is much less satisfactory when one of the substituents is hydrogen or chlorine 15), and it does not seem to have been tested with more heavily functionalised systems. 

Alkyl bromides and iodides are converted into the corresponding fluorides in good yield with mercury(I) fluoride.31 36 Fluorinations of polyhalides are complicated by elimination reactions which give a mixture of alkenes and fluorination products. The fluorinating ability ofmercury(l) fluoride can be increased by the addition of bromine or iodine which results in the formation of mercury(II) fluorohalide.37 38 An example of the reaction of mercury(I) fluoride with simple perfluoroalkyl iodides is the formation of 2//.2//-octafluorobutane (12).39... 

Olefins, addition—Continued of diazoacetic ester, 498 of halo ethers, 232 of halogen, 106 of hydrogen cyanide, 603 of hydrogen halide, 105 of hypohalous acid, 109 of polyhalides, 107 to cyanides, 571 allylic bromination, 36, 104 condensation, with halides, 108 with phenols, 179 conversion to amides (Wi 11 gerodt),... 

Since the polyhalide ions are formed by the addition of diatomic halogen molecules or of interhalogen molecules to a halide ion, the total number of halogen atoms in such a complex is always odd. The most common case is that of the trihalides. Some penta-, hepta-, and enneahalides are likewise known. The highest known polyhalogen complex is PCUBr 1 the structure of this has not been determined, but by analogy to other similar complexes it can probably be expressed as [PClsBr]+[Bri7]. Table I lists the known polyhalide ions. 

Shvo Y, Green R (2003) Addition of a-polyhalides to olefins under mild reaction conditions, catalyzed by Mo(CO)6. J Organomet Chem 675 77-83... 

Iodine forms the most extensive group of polyhalide anions, with triiodide, I3, being the best-known example. The formation of this anion is responsible for the increased solubility of I2 in water on addition of potassium iodide (KI). Triiodide is used extensively in analytical chem-isfly, many analytical procedures being based on the release or uptake of iodine and its subsequent titration with sodium thiosulfate (iodometry). The largest polyhalide anion known, Ijg, consists of an alternate arrangement of triiodide anions and neutral iodine molecules. 

Lewis acid catalyst is normally required when ammonium polyhalides are used, although recourse does not have to be made to strong acids, such as aluminium trichloride. Bromination and iodination reactions are normally conducted in acetic acid in the presence of zinc chloride [32], but chlorination using the ammonium tetrachloroiodate in acetic acid does not require the additional presence of a Lewis acid [33]. Radical chlorination of toluenes by benzyltrimethylammonium tetrachloroiodate in the presence of AIBN gives mixtures of the mono-and dichloromethylbenzenes [34], Photo-catalysed side-chain chlorination is less successful [35], Radical bromination using the tribromide with AIBN or benzoyl peroxide has also been reported [36, 37],... 

Iodine monobromide, like the other binary halogen compounds, has the faculty of forming polyhalides additively. They are obtained by the soln. of the halogen halide in a cone. soln. of the alkali halide salts. Thus, H. L. Wells and S. L. Pen-field 31 prepared KBr.IBr, CsCl.IBr, CsBr.IBr, RbBr.IBr, etc. Since CsBr2I is more stable than CsBrI2. it follows that it is the mutual affinity of the halogens themselves, rather than the volatility of the contained halogen, which determines the stability. 

When iodine is dissolved in hydriodic acid or a soln. of a metallic iodide, there is much evidence of chemical combination, with the formation of a periodide. A. Baudrimont objected to the polyiodide hypothesis of the increased solubility of iodine in soln. of potassium iodide, because he found that an extraction with carbon disulphide removed the iodine from the soln. but S. M. Jorgensen showed that this solvent failed to remove the iodine from an alcoholic soln. of potassium iodide and iodine in the proportion KI I2, and an alcoholic soln. of potassium iodide decolorized a soln. of iodine in carbon disulphide. The hypothesis seemed more probable when, in 1877, G. S. Johnson isolated cubic crystals of a substance with the empirical formula KI3 by the slow evaporation of an aqueous-alcoholic soln. of iodine and potassium iodide over sulphuric acid. There is also evidence of the formation of analogous compounds with the other halides. The perhalides or poly halides—usually polyiodides—are products of the additive combination of the metal halides, or the halides of other radicles with the halogen, so. that the positive acidic radicle consists of several halogen atoms. The polyiodides have been investigated more than the other polyhalides. The additive products have often a definite physical form, and definite physical properties. J. J. Berzelius appears to have made the first polyiodide—which he called ammonium bin-iodide A. Geuther called these compounds poly-iodides and S. M. Jorgensen, super-iodides. They have been classified 1 as... 

In addition to the polyhalide ions discussed previously, which were all anionic, there are comparable cationic species known, although they have been studied considerably less. Many pure interhalogen compounds arc thought to undergo autoionization (see Chapter 10) with the formation of appropriate cationic species ... 

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