Carbon-halogen bonds, reductive metal

Reduction of carbon-halogen bond by metal yields carbanion. Reaction of alkyl halide with Mg in the presence of anhydrous ether as solvent generates Grignard reagent. The Grignard reagent behaves like a carbanion. Alkyllithiums are also obtained from alkyl halides and behave as carbanions. 

Both Ni and Pd reactions are proposed to proceed via the general catalytic pathway shown in Scheme 8.1. Following the oxidative addition of a carbon-halogen bond to a coordinatively unsaturated zero valent metal centre (invariably formed in situ), displacement of the halide ligand by alkoxide and subsequent P-hydride elimination affords a Ni(II)/Pd(ll) aryl-hydride complex, which reductively eliminates the dehalogenated product and regenerates M(0)(NHC). ... 

Cobalt represents an interesting contrast to the many activated metal powders generated by reduction of metal salts. As will be seen, the cobalt powders are highly reactive with regard to several different types of reactions. However, in contrast to the vast majority of metals studied to date, it shows limited reactivity toward oxidative addition with carbon halogen bonds. 

In marked contrast to the majority of activated metals prepared by the reduction process, cobalt showed limited reactivity toward oxidative addition with carbon halogen bonds. Iodopentafluorobenzene reacted with 2 to give the solvated oxidative addition products CoL and Co(C,F5)2 or Co(C F )L The compound CoiOJF 2PEt, was isolated in 54% yield by addition of triethylphosphine to tne solvated materials. This compound was also prepared in comparable yield from 1 by a similar procedure. This compound had previously been prepared by the reaction of cobalt atom vapor with C6F5I(81). 

II. REDUCTIVE METAL INSERTION INTO CARBON-HALOGEN BONDS... 

A. Reductive Metal Insertion into Carbon-Halogen Bonds. 438... 

The mechanism of the Stille reaction involves an oxidative addition of the palladium(O) species into the carbon-halogen bond, a trans-metallation reaction with the organostannane and a final reductive elimination step releasing the product and thereby regenerating the palla-dium(O) catalyst. 

The major reason for using transition-metal catalysts in the intermolecular coupling of aryl halides is to minimize the competition from further reduction of the radical formed by carbon-halogen bond cleavage of the radical anion. The competition from further reduction is less severe when a suitably proximate second aryl group is present, which may react... 

Transition-metal catalyzed metathesis of carbon-halogen bonds with Si-Si bonds provides useful access to organosilicon compounds. Most of the reaction may involve initial oxidative addition of the carbon-halogen bond onto the transition-metal followed by activation of the Si-Si bond to give (organosilyl)(orga-no)palladium(II) complex, which undergoes reductive elimination of the carbon-silicon bond. 

A wealth of information on the reduction of metal ions in aqueous solutions has been obtained and a compilation was published in 1988 [20], However, alkali or alkaline earth metal ions such as Li Na or cannot be reduced by the hydrated electron in aqueous solution but can form an ion pair with the solvated electron in polar liquids. Among the various reactions of the solvated electron, the reduction of halogenated hydrocarbons is often used in radiation chemistry to produce well-defined radicals because of the selective cleavage of the carbon-halogen bond by the attack ofthe solvated electron. This reaction produces the halide ion and a carbon-centered radical, and is of great interest for environmental problems related to the destruction of halogenated organic contaminants in water and soil [21,22]. 

Metallic bronze fh(N 11, ), can, furthermore, be prepared from calcium-ammonia solution by evaporation of the ammonia. A bronze sohd is obtained, which in TH F at -30 °C behaves as a sohd surface in its reaction with alkyl hahdes (Scheme 4.17) [39]. Its apphcation in the reduction of 61 b produces a mixture of cyclopropane derivative 62 (81%) and straight-chain diphenylbutane 64 (8%). The process involves the formation of a tight anion radical-cation radical as an intermediate. Carbon-halogen bond cleavage occurs on the surface of the metalhc cluster. 

A common procedure for the synthesis of organometallic compounds is the reduction of a carbon-halogen bond with a metal (M), as illustrated in Eq. (3.2). This simple equation ignores the role of solvent molecules and aggregated species in some of these reactions ... 

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