Bis 9-carboranyl

The condensation of o- or w-carborane with tellurium tetrachloride in refluxing dichloromethane in the presence of aluminum trichloride produced 9-carboranyl tellurium trichlorides3 4. To facilitate the isolation of the tellurium compounds, the crude product was reduced with sodium sulfide in ethanol to the bis[9-carboranyl] ditellurium derivatives that were obtained as dark-red, air-stable crystals. 

Sodium ortho- and we/a-9-carboranetellurolates3 are obtained by reduction of the bis[9-carboranyl] ditellurium derivatives with sodium borohydride in a 2 1 mixture of ethanol/benzene at 40°. 

The purified bis[9-e>-carboranyl] ditellurium was reacted in dichloromethane with the stoichiometrically required amount of thionyl chloride to produce the 9-o-carboranyl tellurium trichloride and with bromine to give the corresponding tellurium tribromide. The tellurium trichloride was reduced with an excess of hydrazine hydrate in ethanol to bis[9-o-... 

Addition of 1.2 equiv of 1 to Ni(PEt3)4 in pentane at 25 °C gave a dark red solution, concomitant with the evolution of gas. Standard workup and crystallization from toluene-pentane gave 9 as a spectroscopically pure, dark red crystalline solid sensitive to air and stable during brief heating to 100-110 °C. The unusual thermal stability of the nickel bis(silyl) compound is attributed to the advantageous properties of the carboranyl unit, including electronic and steric effect. 

In 2007, we reported the high-yield synthesis of closo- and mrfo-carborane containing Fiechet-type aryl ether cores, which exhibited photoluminescent (PL) properties. The reaction of oc, o -bis-(3,5-bis(bromomethyl)phenoxy-p-xylene with 4 equiv. of the monolithium salt of l-R-l,2-c/o50-C2B,oH,2 (R = CHj, CgHj) in THF, after 24 h. at reflux, gave the corresponding neutral carboranyl-functionalized aryl ether derivatives, in 82% and 85% yield, respectively (Scheme 27.9). Subsequently, closo clusters... 

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