Bis silyl Mercurials

Formation of Silicon-Transition and Inner Transition-Metal Bond 5.8.3.5. from Bis(silyl) Mercurials... 

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

Previously, trifiuorosilyl groups have been bound to phosphorus 40) and silicon via the SiF2(g), fluorine-bond insertion-mechanism 41). The new compound Hg(SiFs)2 is readily hydrolyzed, but it can be stored for long periods of time in an inert atmosphere. It is a volatile, white solid that is stable up to at least 80°C. The preparation of bis(trifluoro-silyl)mercury, of course, raises the possibility of (a) synthesis of the complete series of trifluorosilyl, "silametallic compounds, as had previously been done for bis(trifluoromethyl)mercury by using conventional syntheses, and (6) transfer reactions similar to those in Section II, as well as (c) further exploration of the metal-vapor approach. The compound Hg(SiF,)2 appears also to be a convenient source of difluoro-silane upon thermal decomposition, analogous to bis(trifluoromethyl)-mercury ... 

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 ... 

Bisnor-S, 123, 124 Bis-o-phcnylenc pyrophosphite, 30 Bis(tribromomethyl)mercury, 30 Bis(trichIoromethyl)mercury, 30 Bis-(2,4,5-trichlorophenyI)carbonate, 55 Bis(trimethy]silyl)acetamide, 30... 

Arylpentafluorophenyl-iodonium Compounds (Scheme 48), Bis[tris(pentafluoro-phenyl)silyl]-mercury and -cadmium ((C4F4)3Si]aCd -t- CFa COjH - (CF3-C02)2Cd-F (C8F5)3SiH. Wasserfreie Trifluoroacetate der Hauptgnippe III [CFj-COjH-r... 

Bis(trimethylsilyl)mercury and pentacarbonyliron react to form bis(trimethyl-silyl)tetracarbonyliron [474] (36 /o m.p. 68°C)... 

Bis[tris(triethylgermyl)silyl] Mercury GeeHgSi CaeHeo [(Et3Ge)3Si]2Hg... 

Other addition reactions Additions involving carbon Copper(I) chloride, 85 Lithium bis(dimethylphenyl-silyl)cuprate, 161 Manganese(III) acetate, 171 Mercury(II) chloride, 175 2-(Phenylseleno)acrylonitrile, 244 Threophos, 298 Additions involving nitrogen Benzeneselenenyl halides, 26 Additions involving oxygen Bis(Tj5-cyclooctadienyl)ruthe-nium(II), 35... 

V,7V-Diethylcarbamoyl trimethylsilane has been prepared by the reaction of bis(trimethylsilyl) sulphide with bis(A,A-diethylcarbamoyl) mercury (Scheme 30)16. Silylation of the carbamoyl cuprate reagent derived from a lithium amide, by addition of copper(I) cyanide and subsequent exposure to carbon monoxide (1 atm), is also effective75,110. Poor to moderate yields of carbamoyl silanes may be isolated by treatment of lithium silylamides with carbon monoxide and methyl iodide, in a reaction sequence involving a nitrogen to carbon silyl shift in an intramolecular silylation (Scheme 31)111. 

When a thin film prepared from poly[(tetraethyldisilanylene)bis(2,5-thienylene)] was irradiated in air with a 6-W low pressure mercury lamp bearing a Vycor filter, the absorption maximum near 340 nm disappeared within 40 min. Poly[(tetraethyldisilanylene)(2,5-thienylene)] also exhibited a rapid UV change when its thin film was irradiated. IR spectra of the resulting films reveal strong absorption bands due to Si-O-H and Si-O-Si bonds at 3300 and 1100 cm [. The formation of the Si-O-H and Si-O-Si bonds can be best explained by the reaction of the silyl radicals generated by homolytic scission of the silicon-silicon bonds in the polymer backbone with oxygen in air. The other polymers are also photoactive,... 

Interestingly, compound 64 undergoes a novel isomerization photo-chemically or thermally producing another type of 1,2-disilacyclobutane. Thus, irradiation of a benzene solution of 64 with a high-pressure mercury lamp with a Pyrex filter gives colorless crystals (99% yield) identified as 1, 1,2,2-tetraphenyl-3-[bis(trimethylsilyl)ethenylidene]-4,4-bis(trimethyl-silyl)-l, 2-disilacyclobutane. Photochemical and thermal transformation of... 

Transition metal carbodiimides, such as MnNCN and CuNCN, and carbodiimides derived from zinc, mercury,silver and thallium are also known. A preceramic polymeric titanium carbodiimide is obtained in the reaction of TiCU with bis(trimethyl-silyl)carbodiimide. Liganded carbodiimidotitanium complexes are obtained in the reaction of CpaTiCla with Me3SnN=C=NSi(i-Pr)3. ° Also, dicyclopentadienyl titanium (IV) diisocyanates are converted into carbodiimides with LiN(SrMe3)2. ... 

Methan Bis-[trimethylsilyl]-brom-mercuri-(dimethyl-ethenyl-silyl)-E19d, 824 (Cl Li/+ HgBr2)... 

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