Publisher Summary This chapter discusses organogold complexes preparation and characterization, their reactions, and their comparisons with those of other metals. The area of organogold chemistry has blossomed in the past ten years. Organogold complexes and gold compounds in general predominantly contain the metal in one of two oxidation states–– namely, gold(I) or gold(III). Complexes of gold(I) containing organic groups only as ligands have been prepared recently for the first time. Alkyl and aryl complexes of the type [AuRL] may also be prepared by the reaction of a halide complex with a Grignard reagent. Vinyl compounds have been prepared from gold(I) halide complexes and Grignard reagents. Bi- and tetranuclear, three-center two-electron gold(I) complexes have been prepared containing polyfluorophenyl groups. The preparations of all of the gold(I) carbene complexes to date have utilized isonitrile precursors, either directly or as intermediates. Reductive elimination of alkanes has been observed from a variety of complexes. The reactions of organogold(I) complexes with benzenethiol and -selenol were shown to proceed by a radical chain mechanism. A number of organogold complexes have been subjected to X-ray crystallographic studies, and sufficient data have been accumulated for meaningful comparisons of bond lengths to be made.

Exchange of mercury by gold in organomercury compounds

The Organic Chemistry of Gold

Multimetallic Gold–Iron Compounds Based on Aurated Ferrocenes

by Transmetallation from Mercury

Reactions in which gold, bound to methyl, ethyl, and 1-cyano-1-ethoxycarbonylpentyl groups in their triphenylphosphinegold(I) derivatives, is displaced therefrom by entering mercury from mercuric or alkylmercuric halides, acetates, or nitrates have been examined kinetically in dioxan, acetone, dimethylformamide, and dimethyl sulphoxide solvents. Most of the mercury-for-gold substitutions are second-order processes, and, where this is so, the effect on rate of changes of the anion in the mercurial, and also the kinetic effect of added salts, make clear that the bimolecular electrophilic mechanism of substitution, SE2, is under observation. However, the reactions in which hold from the cyano(ethoxycarbonyl)pentylgold complex is replaced by mercury in solvents containing dimethyl sulphoxide are kinetically of first order in the gold complex, and zeroth order in the mercurial. They illustrate the unimolecular electrophilic mechanism, SE1. In this mechanism all mercurials react at the same rate, which is the rate of formation of a carbanion by heterolysis of the carbon–gold bond. The reaction between mercuric bromide and one gold(III) complex, viz. trimethyl(triphenylphosphine)gold(III), has been examined. In dioxan and acetone as solvents, the gold is displaced from one methyl group only, to be replaced by mercury in an SE2 process.

Mechanism of electrophilic substitution at a saturated carbon atom. Part XI. Bimolecular and unimolecular substitution of mercury for gold in alkylgold complexes

Exchange of mercury by gold in organomercury compounds

Citations

The Organic Chemistry of Gold

Multimetallic Gold–Iron Compounds Based on Aurated Ferrocenes

by Transmetallation from Mercury

References

Mechanism of electrophilic substitution at a saturated carbon atom. Part XI. Bimolecular and unimolecular substitution of mercury for gold in alkylgold complexes

Reactivity of carbon-metal bonds in organogold(I) complexes containing o-vinylphenyl and o-allylphenyl ligands

Related Papers (5)

Reactions of 1-iodosilatrane with organomercury compounds

199Hg chemical shifts in some mercury-containing biheteroorganic compounds

Reaction of free radicals with unsymmetrical organomercury compounds

Direct c-mercuration of barenes with organomercury hydroxides

Effect of electron-donor compounds on the reactions of organomercury compounds with polychloromethanes