Organosilver compounds

See also page 460, Section 2.29, page 475, Section 3.1 and page 484, Section 3.7. 

---

An alternative, but considered (192) a less likely possibility, was that Ru NO induced radical decomposition the case of an organosilver compound was cited as precedent (190). However, we note that in that work a nitroxide and not a spin trap was used. 

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... 

The use of silver acetylides to effect useful synthetic transformations has been perhaps more widely reported than the use of any other organosilver compound, as previously reviewed by Pale et al.81 and Sladkov et al.82 Their use, however, in comparison to that of other metal acetylides (Na, Cu, Li), has perhaps been limited by their relatively low reactivity and/or solubility. The silver acetylides are, however, generally comparatively more stable than the more commonly used metal acetylides, as they can be... 

Silver acetylides undergo oxidative condensation in the presence of cupric chloride to give diynes.124 Dimerization is a reaction common to a number of organosilver compounds, including both alkyl- and arylsilver derivatives. 

In conclusion, it is clear that much scope remains for the development of methodology that exploits the unique chemistry of organosilver compounds. From the methods... 

Schmidbaur, H. Bayler, A. Synthesis and uses of organosilver compounds, in The Chemistry of Organic Derivatives of Gold and Silver, Patai, S. Rappoport, Z., eds., Wiley, Chichester, UK, 1999, pp. 211-226. 

Table 35. Fluorinated Organomercury, Organoarsenic, and Organosilver Compounds...

Chelation has been used to stabilize organosilver compounds. The compound 2-[(dimethylamino)methyl]-phenyl silver, a chelate involving N and C coordination, melts at 180 °C. The adduct with AgBr is light and air stable for 10 days. The product from LiBr was the first example to contain bridging phenyl groups. It decomposes at 180°C but is air and moisture sensitive. 

Organic halides react with metallic Ag, e.g., PhaCCl with Ag foil , but the organosilver compounds cannot be isolated. 

The metal-metal exchange reaction (a) also can be applied to the synthesis of pure organosilver compounds The available AgN03 should not be used as a starting... 

---