Reaction with organomercury halides

Historically, the first report of the Pd-catalyzed cross-conpling reaction with acyl halide used organomercury compounds. " Although alkyl- and arylmercnry chlorides did not work, the use of dialkyl- and diarylmercury componnds gave the desired ketones in good yields. Acyl bromides are necessary to bring about fruitful results. The use of HMPA as the solvent is also unavoidable (Scheme 9). 

The activation entropy for thermal decomposition of /ra j -[MnX(CO)3(PPh3)2] indicates that manganese-phosphorus bond breaking is rate-determining. The rate law for the decomposition of CoH(CO)4 to Co2(CO)8 plus hydrogen is second-order in cobalt compound. While this decomposition has previously been studied in the gas phase, this is the first report of decomposition kinetics in the liquid phase. The first step in reaction of Co2(CO)s with organomercury halides is solvent-induced disproportionation of the dimeric carbonyl. ... 

As for the synthesis of ort/io-phenylene indium complexes, the transmetallation reactions of organomercurials with indium(I) halides have also been considered for the preparation of 1,8-naphthalenediyl diindium complexes. While the dimercura-cycle 62 fails to react with InBr, l,8-bis(chloromercurio)naphthalene (25) and 1,8-bis(bromomercurio)naphthalene (63) react with their respective indium(I) halides to yield the mercura-indacycles 64 and 65 (Scheme 25) which have been isolated as bis(THF) adducts. The indium center of 65-(THF)2 is penta-coordinated and... 

Unsymmetrical diaryl ketones are obtained by the reaction of iodobcnzene with nickel carbonyl in the presence of an organomercury halide ... 

Many other types of organometallics which are not acylated directly acid chlorides and which do not undergo addition to ketones may still transmetallate into the acylpalladiumfll) complex. Simple alkyl organomercurials have been acylated in this fashion to give moderate to good yields of ketones. " Larock has studied the palladium-catalyzed acylation of vinylmercury(II) compounds with acyl halides (equation 104). The reaction was only modestly productive and could not compare to the yield provided by aluminum chloride catalysis. 

This method is less useful preparatively because in most cases the required organomercurials are obtained by the reaction of organomagnesium-halide reagents with mercury(II) halides ... 

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