Synthesis of Organometallic Compounds of Group IV, V, and V Typical Elements and Their Application for C-C Bond Formation

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1. Transition metal-catalyzed hydrometalation(Si,Ge,Sn) of terminal acetylenes. In the presence of RhCl(CO)(PPh_3)_2, PHC CD reacts with Bu_3SnH regio-and stereo-specifically to give (E)-Ph(Bu_3Sn)=CHD. The rhodium-catalyzed hydrogermination and hydrosilylation of RC CH also regiospecifically give R(R'_3M)C=CH_2(M=Ge,Si) in contrast to the platinum-catalyzed hydrosilylation. The most effective catalyst is Rh(acac)(CH_2=CH_2)_2.2. Palladium-catalyzed aryldemetallation of alkenylmetal compounds. Syn-addition of Ar-Pd to double bond and anti-elimination of Pd-SnR_3 play an important role in the palladium-catalyzed aryldestannylation of (E)-Ph(Bu_3Sn)C=CHD with ArN_2BF_4 giving (Z)-PhcH=CDAr Ar-Pd-X aryldestannylate PhcH=CHSnPh_3 by addition-elimination mechanism or transmetallation mechanism depending on the sub-stituents on the aryl group and the ligands of palladium. Facile aryldesilylation and aryldegerminylation were obaserved in the palladium-catalyzed reaction of ArN_2BF_4 with alkenylsilanes and alkenylgermanes, respectively. A reaction of RCH=CHMR'_3(M=Si, Ge) with Ar-Pd-OAc give arylated products, RCH=C(Ar)MR'_3.3. Synthesis of unsymmetrical diaryltellurium from Ar'N_2BF_4 and ArTeH. An addition of Ar'N_2BF_4 to a solution of ArTeH prepared from ArTeTeAr-NaBH_4 or ArTeMgBr-H_2O system yields unsymmetrical disryltellurium in moderate to good yields.