Organosilvers reactions with

It was postulated that organosilver radicals were formed by reaction of CH2OH radicals with Ag+ cations. In order to solve a problem of organosilver radicals structure we carried out the experiments with 109Agi-NaA zeolite exposed to 13CH3OH. 

Allenic alcohols with a variety of allene substitution patterns form 2-alkenyltetrahydropyrans by a 6-exo ring closure upon cyclization with silver or mercury salts (equation 91 ).209 The organosilver intermediate undergoes protiodemetallation under the reaction conditions, while the vinylmercury... 

Kauffmann and coworkers have described the reaction of alkylsilver compounds with cyclohexenone (Scheme 1.6).29 It was found that the alkylsilver derivatives reacted preferentially, and in some cases exclusively, in the (3 position. A significant amount of 3-methylcyclohex-2-enol was observed for the reaction of Me2AgMgBr, which has been attributed to the elimination and subsequent reaction of silver(I) hydride. Silver(I) hydride has been observed in the gas-phase fragmentation of other organosilver compounds.30... 

As is general for organosilver compounds, perfluorophenylsilver is considerably more stable than phenylsilver.55 The first example of a perfluoroarylsilver compound was reported by Miller and Sun in 1970.49 Reaction of perfluorophenyllithium with silver trifluoroacetate, or of perfluorophenyl bromide with perfluoroisopropylsilver, gave perfluorophenylsilver as colorless crystals (Scheme 1.17). The compound was found to be stable up to 150°C, at which temperature it slowly dimerized to give perfluorobiphenyl and metallic silver. Since this initial report a number of syntheses of perfluorophenylsilver from perfluorophenyllithium followed.56,57... 

For mechanistic investigations on Pd/Ag-catalyzed enyne or arylyne synthesis, Pale et al. mixed various alkynylsilvers with vinyl Inflates or aryl iodides in the presence of palladium salts or complexes (Scheme 10.66).105 This reaction clearly demonstrated that organosilvers can be transmetalated to organopalladium species, even if no halide was present, as demonstrated when starting from vinyl triflates. 

The reaction of organolithiums or organomagnesium halide reagents with silver halides produces organosilvers, but these are less stable than those containing Cu and Au and readily decompose to form homo-coupled products via alkyl radicals ... 

The transmetallation reaction between AgBF4 and a tertiary bis(silyl)pyridylmethylh-thium compound afforded the dinuclear alkylsilver species (1), which is stable at room temperature for several days7. Despite the susceptibility of most organosilver compounds to hydrolysis, the argentate complex with a /S-disulphone carbanion (2) can be obtained by the reaction of 1,3-dithiane 1,1,3,3-tetraoxide with silver nitrate in alkaline aqueous solution8. 

Stable organosilver derivatives of chloroferrocene have been prepared by the reaction of the corresponding boronic acid with silver salts in aqueous ammonia solution (equation 32)86 - 88 2-Silver(dimethylaminomethyl)ferrocene has been obtained by trans-metallation between silver bromide and the corresponding lithium ferrocenyl compound89. 

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