Dinuclear Ruthenium Complexes Bearing Dicarboxylate and Phosphine Ligands. Acceptorless Catalytic Dehydrogenation of 1-Phenylethanol
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- 作者：Jeroen van Buijtenen ; Jan Meuldijk ; Jef A. J. M. Vekemans ; Lumbertus A. Hulshof ; Huub Kooijman ; and Anthony L. Spek
- 刊名：Organometallics
- 出版年：2006
- 出版时间：February 13, 2006
- 年：2006
- 卷：25
- 期：4
- 页码：873 - 881
- 全文大小：182K
- 年卷期：v.25,no.4(February 13, 2006)
- ISSN：1520-6041
文摘
Reaction of RuH2CO(PPh3)3 with tetrafluorosuccinic acid at 100 
C gave rise to the formation of thedinuclear bis(tetrafluorosuccinate)-bridged Ru(II) complex 2, containing two water ligands. Exchange ofthe PPh3 in complex 2 with various diphosphine ligands afforded a series of analogous complexes 3.Reaction of the latter with 1-phenylethanol at 130 C or with 2-propanol/Et3N at room temperaturefurnished the dinuclear dihydrido-bridged Ru(II) complexes 4. Complexes 2 and 4 were characterized byX-ray diffraction analysis. Both bis(tetrafluorosuccinate)-bridged complexes 3 and dihydrido-bridgedcomplexes 4 catalyze the acceptorless dehydrogenation of 1-phenylethanol to acetophenone and dihydrogenwith good yields and excellent selectivity under relatively mild conditions in the absence of acid or base.A tentative catalytic cycle for the dehydrogenation of secondary alcohols by Ru(II) complexes of type 3is presented.
C gave rise to the formation of thedinuclear bis(tetrafluorosuccinate)-bridged Ru(II) complex 2, containing two water ligands. Exchange ofthe PPh3 in complex 2 with various diphosphine ligands afforded a series of analogous complexes 3.Reaction of the latter with 1-phenylethanol at 130 C or with 2-propanol/Et3N at room temperaturefurnished the dinuclear dihydrido-bridged Ru(II) complexes 4. Complexes 2 and 4 were characterized byX-ray diffraction analysis. Both bis(tetrafluorosuccinate)-bridged complexes 3 and dihydrido-bridgedcomplexes 4 catalyze the acceptorless dehydrogenation of 1-phenylethanol to acetophenone and dihydrogenwith good yields and excellent selectivity under relatively mild conditions in the absence of acid or base.A tentative catalytic cycle for the dehydrogenation of secondary alcohols by Ru(II) complexes of type 3is presented.