Bis(allyl)-Ruthenium(IV) Complexes as Highly Efficient Catalysts for the Redox Isomerization of Allylic Alcohols into Carbonyl Compounds in Organic and Aqueous Media: Scope, Limitations, and Theoretic
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- 作者：Victorio Cadierno ; Sergio E. Garcí ; a-Garrido ; José ; Gimeno ; Adriá ; n Varela-Á ; lvarez ; and José ; A. Sordo
- 刊名：Journal of the American Chemical Society
- 出版年：2006
- 出版时间：February 1, 2006
- 年：2006
- 卷：128
- 期：4
- 页码：1360 - 1370
- 全文大小：332K
- 年卷期：v.128,no.4(February 1, 2006)
- ISSN：1520-5126
文摘
The catalytic activity of the bis(allyl)-ruthenium(IV) dimer [{Ru(
3:3-C10H16)(
-Cl)Cl}2] (C10H16= 2,7-dimethylocta-2,6-diene-1,8-diyl) (1), and that of its mononuclear derivatives [Ru(3:3-C10H16)Cl2(L)](L = CO, PR3, CNR, NCR) (2) and [Ru(3:3-C10H16)Cl(NCMe)2][SbF6] (3), in the redox isomerization ofallylic alcohols into carbonyl compounds, both in tetrahydrofuran and in water, is reported. In particular, avariety of allylic alcohols have been quantitatively isomerized using [{Ru(3:3-C10H16)(-Cl)Cl}2] (1) ascatalyst, the reactions proceeding in all cases faster in water. Remarkably, complex 1 has been found tobe the most efficient catalyst reported to date for this particular transformation, leading to TOF and TONvalues up to 62 500 h-1 and 1 500 000, respectively. Moreover, catalyst 1 can be recycled and is capableof performing allylic alcohol isomerizations even in the presence of conjugated dienes, which are known tobe strong poisons in isomerization catalysis. On the basis of both experimental data and theoreticalcalculations (DFT), a complete catalytic cycle for the isomerization of 2-propen-1-ol into propenal isdescribed. The potential energy surfaces of the cycle have been explored at the B3LYP/6-311+G(d,p)//B3LYP/6-31G(d,p) + LAN2DZ level. The proposed mechanism involves the coordination of the oxygenatom of the allylic alcohol to the metal. The DFT energy profile is consistent with the experimental observationthat the reaction only proceeds under heating. Calculations predict the catalytic cycle to be stronglyexergonic, in full agreement with the high yields experimentally observed.
3:3-C10H16)(-Cl)Cl}2] (C10H16= 2,7-dimethylocta-2,6-diene-1,8-diyl) (1), and that of its mononuclear derivatives [Ru(3:3-C10H16)Cl2(L)](L = CO, PR3, CNR, NCR) (2) and [Ru(3:3-C10H16)Cl(NCMe)2][SbF6] (3), in the redox isomerization ofallylic alcohols into carbonyl compounds, both in tetrahydrofuran and in water, is reported. In particular, avariety of allylic alcohols have been quantitatively isomerized using [{Ru(3:3-C10H16)(-Cl)Cl}2] (1) ascatalyst, the reactions proceeding in all cases faster in water. Remarkably, complex 1 has been found tobe the most efficient catalyst reported to date for this particular transformation, leading to TOF and TONvalues up to 62 500 h-1 and 1 500 000, respectively. Moreover, catalyst 1 can be recycled and is capableof performing allylic alcohol isomerizations even in the presence of conjugated dienes, which are known tobe strong poisons in isomerization catalysis. On the basis of both experimental data and theoreticalcalculations (DFT), a complete catalytic cycle for the isomerization of 2-propen-1-ol into propenal isdescribed. The potential energy surfaces of the cycle have been explored at the B3LYP/6-311+G(d,p)//B3LYP/6-31G(d,p) + LAN2DZ level. The proposed mechanism involves the coordination of the oxygenatom of the allylic alcohol to the metal. The DFT energy profile is consistent with the experimental observationthat the reaction only proceeds under heating. Calculations predict the catalytic cycle to be stronglyexergonic, in full agreement with the high yields experimentally observed.