Bis-trimethylsilyl mercury

The first organosilylmagnesium compound (Mg(SiMe3)2l.(-CH20Me)2, was isolated in 1977 it was obtained as colourless, spontaneously flammable crystals by reaction of bis(trimethylsilyl)mercury with Mg powder in... 

Bis(trimethylsilyl)hydrazine, 2612 Bis(trimethylsilyl)mercury, 2589 Bis(trimethylsilylmethyl)magnesium, 3093... 

Bis(trimethylsilyl)mercury, 2589 Chloratomercurio(formyl)methylenemercury(II), 0650 Chloromercuriodiphenylgold, 3466... 

The action of liquid sodium amalgam on trimethylchlorosilane (34a, 34b) or -bromosilane (207) at room temperature results in the exclusive formation of bis(trimethylsilyl)mercury, [(CH3)3Si]2Hg, which is relatively stable to heat. This compound, however, undergoes decomposition on heating at 100°-160° C for a day to give hexamethyldisilane in quantitative yield (9, 34a, 34b, 207). 

A reaction mechanism via silyl radicals is plausible12Bettler, Sendra and Urry37, 64s treated bis(trimethylsilyl)mercury with SiHCl3 , ... 

Bis(trimethylsilyl)mercury (a convenient source of Sime3 groups in organo-metallic reactions) was successfully used by Glockling for the preparation of trimethylsilyl complexes of platinum ... 

Reactions of simple pyridines with bis(trimethylsilyl)mercury results in the formation of l,r-bis(trimethylsilyl)-l,l, 4,4 -tetrahydro-4,4 -bipyridines. These reversibly dissociate on heating in oxygen-free solution to yield 1-trimethylsilyl-l-hydropyridinyl radicals which have been characterized by ESR, e.g., 71 for which splittings are given in gauss.241 If the pyridines bear... 

The structure of 5 was confirmed by metathesis of dimethyldiacetoxysilane with perfluoropinacol 108). The reactions according to Eqs. (8) and (9) proceed via the alkali salts of perfluoropinacolate dianion, which in the case of sodium can be obtained as a pure white powder 153). Compound 4 is also accessible by reaction of HFA and bis(trimethylsilyl)mercury under mild conditions 153). As the reaction rate is increased by UV radiation, formation of trimethylsilyl radicals is assumed to be the first step. 

Bis-trimethylsilyl mercury 419 reacts with carbodiimides to give insertion products 420. ... 

Trimethyl(perfluorophenyl)silanc (1) is synthesized by the reaction of the Grignard reagent obtained from bromopentafluorobenzene and magnesium, with chlorotrimethylsilane in diethyl ether (90% yield), or by irradiation of a mixture of bis(trimethylsilyl)mercury and perfluoro-phenylmercury bromide (40% yield). " ... 

Bis(trimethylsilyl)mercury a Powerful Reagent for the Synthesis of Amino Carbenes... 

Keywords amino carbene, bis(trimethylsilyl)mercury, chloroiminium salt... 

Summary Bis(trimethylsilyl)mercury cleanly reacts at low temperature with chloroiminium chlorides to form stable metal-free cyclic and acyclic diaminocarbenes as well as aryl-, oxy-, chloro-, hydrogeno- and alkyl-amino carbenes. The aryl-, chloro-and hydrogeno-amino carbenes were formed as transient intermediates that undergo dimeri2ation into the corresponding alkenes, which were isolated in good yields. Alkyl-and oxy-amino carbenes were observed at low temperature by C NMR spectroscopy. 

General reaction of a chloroiminium chloride with bis(trimethylsilyl)mercury. 

For this reaction, we added a solution of bis(trimethylsilyl)mercury (in THF) to the suspension of the chloroiminium salt in THF at low temperature and allowed the reaction mixture to warm to room temperature. After about one hour, we obtained a clear yellow solution and a drop of mercury. After separation of the metal and evaporation of the solvent the carbene was isolated. 

In our quest to prepare new aryl amino carbenes, we reacted A-diisopropyl-C-phenyl chloroiminium chloride with bis(trimethylsilyl)mercury in THF. The reaction was monitored by C NMR spectroscopy at -78 °C, but the carbene was not observed. Instead, the dimer was formed as a 90/10 mixture of E and Z isomers. 

In a more reckless attempt to prepare an amino hydrogeno carbene, we performed a reaction between bis(trimethylsilyl)mercury and IV-diisopropyl-C-chloro aldiminium chloride. Not surprisingly, even at low temperature we observed the direct formation of the dimer. 

Starting from the chloroiminium salt we performed the reaction with bis(trimethylsilyl)mercury at low temperature in THF. 

When bright yellow, solid bis(trimethylsilyl)mercury is treated with trimethylsilyl-lithium in 1,2-dimethoxy ethane (DME), color changes occur and either a three- or a four-coordinated anionic silyl-Hg compound may be isolated according to the stoichiometry ... 

Although in these complexes the cations are solvated, it is possible to desolvate them without decomposition. Similarly, alkali metals react with bis(trimethylsilyl)mercury ... 

Bis(trimethylsilyl)mercury is prepared by shaking together 1 % Na amalgam with either neat MejSiCl or its cyclohexane solution. An inert atmosphere is essential, although (Me3Si)2Hg is stable to H2O. The yield is greater if MejSil or McjSiBr is used, but the commercial availability of MCjSiCl and its low cost offset this advantage ... 

I,2-Bis(hydroxomercurio)-I,I,2,2-bis(oxydimercurio)ethane, 0708 Bis- 7(imidosulfurdifluoridato)mercury, 4342 Bis(trimethylsilyl)mercury, 2593... 

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