Carbon-halogen complex

Secondary alkyl halides react by a similar mechanism involving attack on benzene by a secondary carbocation Methyl and ethyl halides do not form carbocations when treated with aluminum chloride but do alkylate benzene under Friedel-Crafts conditions The aluminum chloride complexes of methyl and ethyl halides contain highly polarized carbon-halogen bonds and these complexes are the electrophilic species that react with benzene... 

Direct halogenation of sucrose has also been achieved using a combination of DMF—methanesulfonyl chloride (88), sulfuryl chloride—pyridine (89), carbon tetrachloride—triphenylphosphine—pyridine (90), and thionyl chloride—pyridine—1,1,2-trichloroethane (91). Treatment of sucrose with carbon tetrachloride—triphenylphosphine—pyridine at 70°C for 2 h gave 6,6 -dichloro-6,6 -dideoxysucrose in 92% yield. The greater reactivity of the 6 and 6 primary hydroxyl groups has been associated with a bulky halogenating complex formed from triphenylphosphine dihaUde ((CgH )2P=CX2) and pyridine (90). 

Both Ni and Pd reactions are proposed to proceed via the general catalytic pathway shown in Scheme 8.1. Following the oxidative addition of a carbon-halogen bond to a coordinatively unsaturated zero valent metal centre (invariably formed in situ), displacement of the halide ligand by alkoxide and subsequent P-hydride elimination affords a Ni(II)/Pd(ll) aryl-hydride complex, which reductively eliminates the dehalogenated product and regenerates M(0)(NHC). ... 

Electrogenerated nickel(I)251 and cobalt(I)252 complexes of Salen (Salen = bis(salicylidene)ethane-1,2-diamine) have displayed good catalytic properties in the cleavage of carbon-halogen bonds in a variety of organic compounds. Recent research in this field has been reviewed.253... 

GeCl2 can be inserted into carbon-halogen bonds upon release from its dioxane complex... 

Hydrodehalogenation - that is, hydrogenolysis of the carbon-halogen bond -involves the displacement of a halogen bound to carbon by a hydrogen atom. This chapter is devoted to dehalogenations mediated by transition-metal complexes (Eq. (1)) ... 

Vinylic halides are virtually unreactive and a high selectivity is to be found in the preferential cleavage of aliphatic carbon-halogen bonds of haloalkanoic amides and esters, and of nitro- and cyanoaryl derivatives. Activated haloarenes, e.g. 1-chloro-2,4-dinitrobenzene, however, give a complex mixture of products [7]. 

Carbon monoxide and low valent transition metals are known to give various quite well described complexes. However, due to the strong coordination to CO, these metal carbonyl compounds are not very reactive towards carbon-halogen bonds. Thus the carbonylation of organic halides remains a difficult reaction since the presence of CO leads to the deactivation of the catalytic system. Various attempts to overcome this drawback have however been reported. 

Carbon-Halogen Bond Reactions Catalysed by Ni, Co and Pd Complexes... 

The catalysis of the cleavage of carbon-halogen bonds by complexation with metal ions such as silver or mercuric ion is a well-known phenomenon. The compounds susceptible to this action are alkyl halides capable of forming car-bonium ions. The complexed anions such as in mercuric nitrate, mercuric perchlorate, or hydrated mercuric ion do not exhibit a simple relationship between their effect on the total rate and on the relative distribution of products stemming from water or the anion. This evidence is indicative of the following catalytic mechanism ... 

An extensive review55 of the chemistry of halogen complexes containing carbon ligands, the hypervalent halogen compounds , has been published recently. This is written from an organic chemical viewpoint and includes discussion of the organic chemistry involved in reactions of these compounds. Only aspects directly related to coordination chemistry will be mentioned here. 

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