Carbon—antimony bonds reactions with

Exchange of antimony-carbon bonds with antimony-halogen bonds in triphenylantimony and antimony trichloride upon heating at 250° C for 75 hours has been utilized for the preparation of phenylantimony chlorides (108,109). Also exchange of vinyl groups with chlorine atoms on antimony has been observed (155). Recently, however, a quantitative study of the kinetics of the reaction between trimethylantimony and antimony trichloride has been reported (298), details of which have been discussed in Section IV, A,1. 

Exchange of antimony-carbon bonds with antimony-oxygen bonds is reported in a thorough study of the disproportionation of arylantimony oxides, RSbO (126, 127). At moderately elevated temperatures ( 100° C) in the solid state, the reaction of Eq. (157)... 

Organic fluorine compounds were first prepared in the latter part of the nineteenth century. Pioneer work by the Belgian chemist, F. Swarts, led to observations that antimony(Ill) fluoride reacts with organic compounds having activated carbon—chlorine bonds to form the corresponding carbon—fluorine bonds. Preparation of fluorinated compounds was faciUtated by fluorinations with antimony(Ill) fluoride containing antimony(V) haUdes as a reaction catalyst. 

Dimethyl ditellurium and tetramethyldistibane formed, within a few minutes at 20° in an exothermic reaction dime thyIstibane methyl tellurium in quantitative yield2. The reaction with tetraethyldistibane is best carried out at — 40° to prevent cleavage of carbon-antimony bonds. 

Replacement of Labile Chlorines. When PVC is manufactured, competing reactions to the normal head-to-tail free-radical polymerization can sometimes take place. These side reactions are few ia number yet their presence ia the finished resin can be devastating. These abnormal stmctures have weakened carbon—chlorine bonds and are more susceptible to certain displacement reactions than are the normal PVC carbon—chlorine bonds. Carboxylate and mercaptide salts of certain metals, particularly organotin, zinc, cadmium, and antimony, attack these labile chlorine sites and replace them with a more thermally stable C—O or C—S bound ligand. These electrophilic metal centers can readily coordinate with the electronegative polarized chlorine atoms found at sites similar to stmctures (3—6). 

Hydrocarbons undergo related reaction.s in the super-acid media, such as fluorosuiphuric acid and antimony pentachloride. It has been suggested that the initial one-electron processes during the electrochemical oxidation of alkanes in fluorosuiphuric acid involve a protonated carbon-hydrogen bond with formation of a carbon radical and release of two protons [15]. 

The antimony analogue of diars, o-phenylenebis(dimethylstibine), has been prepared, as has its phenyl analogue (equation 43).162 Attempts to prepare multidentate stibines have been unsuccessful, probably due to the weaknes of the carbon-antimony bond. For example, in the reaction of BunLi with o-C6H4(SbPh2)Br the nucleophile attacks the C—Sb as well as the C—Br bond.142... 

Carbon functional groups, attachment to polysilanes, 3, 585 Carbon-heteroatom bond formation via antimony(III) compounds, 9, 428 via antimony(V) compounds, 9, 432 via bismuth(III) compounds characteristics, 9, 440 with copper catalysts, 9, 442 non-catalyzed reactions, 9, 443 with bismuth(V) compounds, 9, 450 with bismuthonium salts, 9, 449 with bismuth ylides, 9, 450 Carbon-heteroatom ligands in tetraosmium clusters, 6, 967 in tetraruthenium clusters, 6, 960... 

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