Metal halides, reaction with compounds

The main synthetic technique for obtaining carbyne complexes is through the reaction of carbene compounds with metal halides, preferably with those of Group IIIA [259c] as, for example, through reaction (2.2) ... 

The (tM—C bond breaking may take place as a result of reactions with compounds containing active hydrogen atoms, with halogens, alkyl halides, hydrogen, metal... 

Remarkably, it has not proved possible to synthesize heterometallic clusters from 53 (the SeSiMe3 derivative of 52) or other transition metal halide derivatives (with the exception of the syntheses of 61 and 62). [158, 159] It has been possible to synthesize larger palladium clusters, however. The reaction of with [CpCrQ2(THF)] or [PdQ2(PPh3)2], for example, has led to the formation of Pdj, Pdy, and Pds complexes (Scheme 3-24). The isolation of these compounds is not an easy task. 

Thallium(III), particularly as the trifluoroacetate salt, is also a reactive electrophilic metalating species, and a variety of synthetic schemes based on arylthallium intermediates have been devised. Arylthallium compounds are converted to chlorides or bromides by reaction with the appropriate cupric halide. Reaction with potassium iodide gives aryl iodides. Fluorides are prepared by successive treatment with potassium fluoride and... 

Many organic halides do not react satisfactorily with lithium to form RLi ecMnpounds or with metallic magnesium to form Grignard reagents. The desired organolithium compound can often be prepared by a halogen-metal interconversion reaction ... 

Phosphoms shows a range of oxidation states from —3 to +5 by virtue of its electronic configuration. Elemental P is oxidized easily by nonmetals such as oxygen, sulfur, and halides to form compounds such as 2 5 2 5 reduced upon reaction with metals to generate phosphides. The... 

Chlorination of OCT with chlorine at 90°C in the presence of L-type 2eohtes as catalyst reportedly gives a 56% yield of 2,5-dichlorotoluene (79). Pure 2,5-dichlorotoluene is also available from the Sandmeyer reaction on 2-amino-5-chlorotoluene. 3,4-Dichlorotoluene (l,2-dichloro-4-methylben2ene) is formed in up to 40% yield in the chlorination of PCT cataly2ed by metal sulfides or metal halide—sulfur compound cocatalyst systems (80). 

Perfluoroalkyl or -aryl halides undergo oxidative addition with metal vapors to form nonsolvated fluonnated organometallic halides and this topic has been die subject of a review [289] Pentafluorophenyl halides react with Rieke nickel, cobalt, and iron to give bispentafluorophenylmetal compounds, which can be isolated in good yields as liquid complexes [290] Rieke nickel can also be used to promote the reaction of pentafluorophenyl halides with acid halides [297] (equation 193)... 

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