Chlorobis methane

The stretched porphycenes have shown some promise as ligands for the com-plexation of transition metal cations. For instance, when [22]tetradehydroporphyrin-(2.2.2.2) 4.115 is treated with di-p-chlorobis[dicarbonylrhodium(I)] in dichloro-methane using potassium carbonate as base, a bis[Rh(CO)2] complex is formed. ... 

Bis(diisopropylamino)phosphanyl(trimethylsilyl)diazomethane 6, easily available by treatment of chlorobis(diisopropylamino)phosphane with lithiated diazo(trimethylsilyl)methane, provides upon flash thermolysis at 250"C the so-called stable carbene 7.38,39,40 behaves partly as a nucleophilic carbene and reacts only with electron-deficient alkenes such as methyl propenoate or diethyl fumarate under cyclopropanation." In the former case only the Z-isomer 8 is formed. Cyclopropane 9 is thermally unstable and is, therefore, oxidized in situ at the phosphorus atom with elemental sulfur to provide cyclopropane 10, Cyclopropanes 8 and 9 are also generated from the diazo compound 6 and the appropriate alkene by photolysis." ... 

Alternate Names chlorobis(trimethylsilyl)methane bis(trime-thylsilyl) methyl chloride bis(trimethylsilyl)chloromethane [chloro(trimethylsilyl)methyl]trimethylsilane. 

Form Supplied in colorless liquid, commercially available. Preparative Method a convenient one-pot procedure has been developed by Kemp and Cowley in which trimethylsilylchlo-ride reacts with dichloromethane in the presence of wBuLi at — 110°C to give bis(trimethylsilyl)dichloromethane. This intermediate is sequentially treated with nBuLi and ethanol to yield chlorobis(trimethylsilyl)methane. A number of other syntheses have been described. - ... 

Purification fractionally distilled through a "Wgreaux column. Handling, Storage, and Precautions flammable. Chlorobis(tri-methylsilyl)methane is irritating to the eyes, skin, and respiratory system and should only be handled in a well-ventilated fume hood. In addition, proper protective clothing, gloves, and eye/face protection should be worn when title compound is in use. In case of contact with eyes, rinse immediately with water and seek medical advice. 

Peterson Oleflnation Reactions. McNulty and Das have shown that the treatment of chlorobis(trimethylsilyl)methane (1) with 5-BuLi at low temperatures favors lithium-halogen exchange processes over deprotonation pathways (eq 1)The resulting lithi-ated derivative 2 undergoes Peterson oleflnation reactions with a... 

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