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.

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。

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”。