| Project/Area Number |
04805084
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| Research Category |
Grant-in-Aid for General Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Research Field |
有機工業化学
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| Research Institution | Tokyo Instltute of Tchnology |
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Principal Investigator |
OSAKADA Kohtaro Research Laboratory of Resources Utilization Assoc.Prof, 資源化学研究所, 助教授 (00152455)
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| Project Period (FY) |
1992 – 1993
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| Project Status |
Completed (Fiscal Year 1993)
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| Budget Amount *help |
¥1,800,000 (Direct Cost: ¥1,800,000)
Fiscal Year 1993: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 1992: ¥1,300,000 (Direct Cost: ¥1,300,000)
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| Keywords | Rhodium complex / Palladlum complex / Thiolato ligand / C-C bond formation / C-S bond formation / Polyaddition / Hydrosilane / 求核試剤 |
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| Research Abstract |
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 equation
2) 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.
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