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

铑和钯的硫代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和C-S键形成的机理，并将金属辅助成键反应发展到有机和聚合物的合成中。所得结果如下：1)乙基钯苯硫代配合物和苯硫代配合物与有机卤化物反应，通过底物的有机基团与苯硫代配体之间的C-S键形成烷基（苯基）硫化物。反应的动力学测量表明，硫化物的形成遵循以下动力学方程：2)在各种钯配合物的存在下，二硫醇与二炔的多加成得到聚（乙烯硫醚）。Pd(OAc)_2和PdCl_2(PhCN)_2(PhCN)_2催化苯二硫醇与1 - omega-diyne的多元加成反应。反应产物主要是硫化乙烯，其结构为-CH= cme - s，似乎是末端炔在S-H键为C=C双键的条件下初始转化成烯而形成的。苯乙硫腙Rh(1)与硅基和硫基配体的配合物。将配合物加热到50ºC以上，定量地观察了铑（III）配合物与二苯基（苯乙酯）硅基配体的形成。反应的动力学结果和氘同位素效应清楚地表明，二苯基（苯乙硫代）硅烷的还原消除和再氧化加成是反应的途径。研究了过渡金属配合物促进咪唑环形成的作用。

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.