Benzene hydrogenation by silica-supported catalysts made of palladium nanoparticles and electrostatically immobilized rhodium single sites

被引：19

作者：

Barbaro, Pierluigi ^{[1
]}

Bianchini, Claudio ^{[1
]}

Dal Santo, Vladimiro ^{[2
]}

Meli, Andrea ^{[1
]}

Moneti, Simonetta ^{[1
]}

Pirovano, Claudio ^{[3
]}

Psaro, Rinaldo ^{[2
]}

Sordelli, Laura ^{[2
]}

Vizza, Francesco ^{[1
]}

机构：

[1] CNR, ICCOM, Area Ric CNR Firenze, I-50019 Florence, Italy

[2] CNR, ISTM, I-20133 Milan, Italy

[3] Univ Milan, Dipartimento CIMA, I-20133 Milan, Italy

来源：

ORGANOMETALLICS | 2008年 / 27卷 / 12期

关键词：

D O I：

10.1021/om800223d

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The complex [Rh(cod)(dppp)]OTf (Rh(cod)) has been immobilized onto silica-supported palladium nanoparticles (Pd/SiO2) via a dual H-bond/ionic interaction (dppp = 1,3-bis(diphenylphosphino)propane; cod = cycloocta-1,5-diene). The product obtained, Rh(cod)-Pd/SiO2, has been employed to catalyze the hydrogenation of benzene to cyclohexane, showing much higher activity as compared to Pd/SiO2, while Rh(cod) grafted on, bare silica (Rh(cod)/SiO2) is totally inactive. The catalyst generated by Rh(cod)-Pd/SiO2 exhibits a remarkable stability and can be recycled several times with no loss of activity, even if exposed to air. In situ and ex situ EXAFS and DRIFTS measurements, batch catalytic reactions under different conditions, deuterium labeling experiments, and model organometallic studies, taken altogether, have provided valuable mechanistic information. The reduction of benzene to cyclohexa-1,3-diene occurs with the cooperation of the two metals, while the rhodium single sites are more effective than the palladium nanoparticles in the hydrogenation of cyclohexa-1,3-diene to cyclohexane.

引用

页码：2809 / 2824

页数：16

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