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

使用亲核 Rh 和 PJ 试剂的 C-C 和 C-S 键形成反应

• 批准号: 04805084
• 负责人: OSAKADA Kohtaro
• 金额: $ 1.15万
• 依托单位: Tokyo Instltute of Tchnology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1992
• 资助国家: 日本
• 起止时间: 1992 至 1993
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-04805084/
• 关键词: Rhodium complex; Palladlum complex; Thiolato ligand; C-C bond formation; C-S bond formation; Polyaddition; Hydrosilane; 求核試剤

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.

Rh和Pd的硫代络合物对有机酸酯和羧酸酯具有亲核反应活性。本研究旨在阐明这些络合物促进C-C和C-S成键的机理，并将金属辅助成键反应发展到有机合成和聚合物合成。得到的结果如下：1)乙基钯的苯硫醇络合物和苯硫醇钠络合物与有机卤化物通过底物的有机基团与苯硫醇配体之间的C-S键反应生成烷基(苯基)硫化物。反应的动力学测量表明，硫化物的生成遵循动力学方程。2)考察了在不同钯配合物存在下，二硫醇与二炔多加成得到聚乙烯硫化物S的反应。Pd(OAc)_2和PdCl_2(PHCN)_2(PHCN)_2催化苯二硫酚与1欧米茄二炔的加成反应。反应产物主要由乙烯硫化物组成，其结构为-CH=cME-S，在此条件下可能是由末端的炔烃初始转化为烯丙烯，然后将S-H键转移到C=C双键。苯硫醇Rh(1)与硅基和硫醇配体都是配位的。将络合物加热到50ﾟC以上，可定量生成Rh(III)与二苯基(苯硫代)硅基配体的络合物。反应的动力学结果，包括反应的还原同位素效应，清楚地表明了二苯基(苯硫基)硅烷的还原消除和还原加成的反应途径。

项目成果

K.Osakada, K.llstsys, and T.Yamamoto: "Rhodium (1) and Rhodium (III) Phosphine Complexes with Non-bridging Benzenethiolato Ligands. Preparation, Structures and Chmical Properties" Inorg.Chem. 32. 2360-2365 (1993)

K.Osakada、K.llstsys 和 T.Yamamoto：“具有非桥联苯硫醇配体的铑 (1) 和铑 (III) 膦配合物。制备、结构和化学性质” Inorg.Chem。

Y.-J.Kim, R.Sato, T.Maruyama, K.Osakada, and T.Yamamoto: "Structure and Reactivity of Aryl(bromo)nickel Complexes Relevant to Nickel Complexes Promoted Dehalogenative Condensation of Organic Haides" J.Chem.Soc., Dalton Trans. (in press). (1994)

Y.-J.Kim、R.Sato、T.Maruyama、K.Osakada 和 T.Yamamoto：“与镍配合物促进有机卤化物脱卤缩合相关的芳基（溴）镍配合物的结构和反应性”J.Chem。

I.Yamaguchi,K.Osakada,T.Yamamoto: "Preparation of Novel Poly(enol ester)s by Ruthenium Complex Catalyzed Polyaddition of Dicarboxylic Acids with Diynes" Macromolecules. 27(in press). (1994)

I.Yamaguchi，K.Osakada，T.Yamamoto：“通过钌配合物催化二羧酸与二炔的加聚制备新型聚（烯醇酯）”大分子。

K.Osakada,K.Hataya,T.Yamamoto et al.: "Preparation and Structure of a Disilarhodacycle,fac-Rh(SiMe_2CH_2CH_2SiMe_2) H(PMe_3)_3" Journal of Chemical Society,Chemical Communications. 576-577 (1993)

K.Osakada、K.Hataya、T.Yamamoto 等人：“二硅罗达环的制备和结构，fac-Rh(SiMe_2CH_2CH_2SiMe_2) H(PMe_3)_3”化学学会杂志，化学通讯。

Y.J.Kim,K.Osakada,T.Maruyama,T.Yamamoto: "Structure and Reactivity of Aryl(bromo)nickel Complexes Relevant to Nickel Complexes Promoted Dehalogenative Polycondensation." Journal of Chemical Society,Dalton Transactions. (in press). (1994)

Y.J.Kim、K.Osakada、T.Maruyama、T.Yamamoto：“与镍配合物促进脱卤缩聚有关的芳基（溴）镍配合物的结构和反应性”。