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

1. 过渡金属催化末端乙炔的金属加氢反应（Si,Ge,Sn）。在RhCl(CO)(PPh_3)_2存在下，PHC CD与Bu_3SnH区立体特异反应生成(E)-Ph(Bu_3Sn)=CHD。与铂催化的硅氢化反应相比，铑催化的RC CH的氢萌发和硅氢化反应也有区域特异性地得到R(R′_3M)C=CH_2（M=Ge,Si）。最有效的催化剂是Rh(acac)(CH_2=CH_2)_2.2。钯催化烯基金属化合物芳基脱金属。在钯催化的(E)-Ph(Bu_3Sn)C=CHD与ArN_2BF_4的芳基乙酰化反应中，Ar-Pd- x芳基乙酰化产物PhcH=CHSnPh_3根据芳基取代基和钯配体的不同，通过加成-消除机制或金属化机制得到(Z)-PhcH=CDAr - pd - x芳基乙酰化产物PhcH=CHSnPh_3， Ar-Pd- pd - x芳基乙酰化产物PhcH=CHSnPh_3。在钯催化的ArN_2BF_4与烯基硅烷和烯基germanes的反应中，分别观察到芳基去硅基化和芳基去萌发化。RCH=CHMR'_3（M=Si, Ge）与Ar- pd - oac反应得到芳基化产物RCH=C(Ar)MR'_3.3。arn_2bf_4和ArTeH合成不对称二芳基碲。在artetetear - nabh_4或ArTeMgBr-H_2O体系制备的ArTeH溶液中加入Ar'N_2BF_4，可制得不对称的二烷基碲，产率中高。

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.