C-C and C-S bond formlng reactlon uslng nucleophilic Rh and PJ reagents

Rh和Pd的硫醇配合物对有机卤化物和羧酸酯具有亲核反应性。本研究的目的是阐明这些配合物促进C-C键和C-S键形成的机理，并将金属辅助成键反应发展到有机合成和高分子合成中。结果表明：1）乙基钯苯硫基配合物和苯硫基噻吩配合物与有机卤化物反应，通过底物的有机基团与tholato配体之间形成C-S键，生成烷基（苯基）硫醚。反应动力学研究表明，硫化物的生成符合动力学方程。2）在不同钯配合物存在下，研究了二硫醇与二炔的聚加成反应。Pd（OAc）_2和PdCl_2（PhCN）_2（PhCN）_2催化苯二硫醇与1 ω-二炔的加成反应。反应产物主要是乙烯基硫醚，其结构为-CH=CMe-S-，它是由末端炔在一定条件下转化为丙二烯，然后S-H键转化为C=C双键而形成的。在50 ℃以上加热可定量生成Rh（III）与二苯基硫代苯甲硅烷基配体的配合物。反应动力学研究表明，反应过程中二苯基（苯硫醇基）硅烷先还原消除，然后再氧化加成，并研究了过渡金属配合物对咪唑环生成的促进作用。

Thiolato complxes of Rh and Pd have nucleophlic reactivity toward organac halydes and carboxylic esters. This study wascarried out for the purose of elucidation of mechanism of C-C and C-S bond formation promoted by these complexes as well as of development of the metal assisted bond forming reaction into organic and polymer synthesis. The results obtained are as follows.1) Ethylpalladium benzenethiolato complexes and benzenethiolato thodium complex react with organic halides to give alkyl(phenyl)sullide through C-S bonf formation bctween the organic group of the substrate and the tholato ligands. Kinetic measurement of the reactions has revealed that formation of the sulfide follows the kinetic equation2) Polyaddition of dithiol with diynes to give poly(vinyl sulfide)s were examined in the presence of various Pd complexes as cetalrst. Pd(OAc)_2 and PdCl_2(PhCN)_2(PhCN)_2 catalyzes bolyaddition of benzenedithiol with 1.omega-diyne. The products of the reaction is mainly somposed of vinyl sulfide having the structure -CH=CMe-S-that seems to be formed through initial conversion of the terminal alkyne to allene under the conditions followed by eddition of the S-H bond to the C=C double bond.Benzenethiolato Rh(1)conplex with both silyl and thiolato ligands. Heating the complex above 50ﾟC canses fornation of Rh(III) complex with a diphenyl(benzenethioato)silyl ligand quantitatively. Kinetic results of the reaction including deutelium isotope effectof the reaclion indicates clearly the reaction pathway involving reductive eliminatin of the diphenyl(benzenethiolato)silane followed by its re-oxdative addition.Transition metal compexes promoted formation of imidazole ring was also investigated.