Preparation and Characterization of Chiral Zerovalent Organoruthenium Aqua Complexes
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- 作者：Yasuyuki Ura ; Fumiaki Tsunawaki ; Kenji Wada ; Masashi Shiotsuki ; Teruyuki Kondo ; Syuhei Yamaguchi ; Hideki Masuda ; Atsushi Ohnishi ; and Take-aki Mitsudo
- 刊名：Organometallics
- 出版年：2005
- 出版时间：November 7, 2005
- 年：2005
- 卷：24
- 期：23
- 页码：5724 - 5731
- 全文大小：304K
- 年卷期：v.24,no.23(November 7, 2005)
- ISSN：1520-6041
文摘
Enantiopure organoruthenium aqua complexes, Ru(dppe)(dmfm)2(H2O) (1) [dmfm =dimethyl fumarate] and Ru(QUINAP)(dmfm)2(H2O) (2) [QUINAP = 1-(2-diphenylphosphino-1-naphthyl)isoquinoline], were prepared and the absolute structures were determined byX-ray crystallography. In the crystals of these complexes, the water molecule is captured inthe chiral coordination environment assisted by two different hydrogen bonds; that is, achiral center is generated on the coordinated oxygen of water. The behavior of the coordinatedwater in 1 and 2 was monitored by variable-temperature 1H NMR measurement. At lowerthan -60 to -70 
C, the nonequivalency of the geminal protons in the coordinated watermolecule was observed even in solution. On the basis of the VT NMR data and DFT study,the behavior of the coordinated water was discussed. Complex 1 reacts with ammonia togive Ru(dppe)(dmfm)2(NH3) (4), which is the first example of the isolated mononuclearRu(0) ammonia complex. Complex 4 was reversibly converted into 1 by the reaction withwater.
C, the nonequivalency of the geminal protons in the coordinated watermolecule was observed even in solution. On the basis of the VT NMR data and DFT study,the behavior of the coordinated water was discussed. Complex 1 reacts with ammonia togive Ru(dppe)(dmfm)2(NH3) (4), which is the first example of the isolated mononuclearRu(0) ammonia complex. Complex 4 was reversibly converted into 1 by the reaction withwater.