| Автор | Standfest-Hauser, Christina |
| Автор | Slugovc, Christian |
| Автор | Mereiter, Kurt |
| Автор | Schmid, Roland |
| Автор | Kirchner, Karl |
| Автор | Xiao, Li |
| Автор | Weissensteiner, Walter |
| Дата выпуска | 2001 |
| dc.description | The syntheses of and catalytic studies on some Ru(ii) complexes bearing the aminophosphine ligands N,N-dimethyl-2-diphenylphosphinoethylamine (PN), optically pure (RC,Spl)-2- {1-(N,N-dimethylamino)ethyl}-1-diphenylphosphinoferrocene (PPFA), and N,N-dimethyl-2-diphenylphosphinoaniline (DBD) are described, [RuCp(CH3CN)3]<sup>+</sup> reacts with these ligands to give the cationic complexes [RuCp(PN-κN,κP)(CH3CN)]<sup>+</sup> (1a), [(SRu,RC,Spl)-RuCp(PPFA-κN,κP)(CH3CN)]<sup>+</sup> (1b), and [RuCp(DBD-κN,κP )(CH3CN)]<sup>+</sup> (1c), respectively, in high yields. From these, in turn, the residual CH3CN ligand can be replaced by Br<sup>â </sup> upon addition of NEt4Br in CH2Cl2, resulting in the formation of the neutral complexes RuCp(PN)Br (2a), (SRu,RC,Spl)-RuCp(PPFA)Br (2b), and RuCp(DBD)Br (2c), again in good yields. Similarly, [Ru(η<sup>6</sup>-p-cymene)Cl2]2 reacts with 1 equiv. of PN or PPFA to give Ru(η<sup>6</sup>-p-cymene)(PN-κP)Cl2 (3a) and Ru(η<sup>6</sup>-p-cymene)(PPFA-κP)Cl2 (3b). Furthermore, treatment of 3 with TlCF3SO3 in THF at room temperature affords the cationic complexes [Ru(η<sup>6</sup>-p-cymene)(PN-κN,κP)Cl]CF3SO3 (4a) and [(RRu,RC,Spl)-Ru(η<sup>6</sup>-p-cymene)(PPFA-κN,κP)Cl]CF3SO3 (4b). The absolute configuration at the metal center of 2b and 4bâ ² (BPh4<sup>â </sup> salt of 4b) was determined by X-ray crystallography. Catalytic studies were performed with the racemic complexes 1a, 2a, 2c, and 4a and the diastereopure complexes 1b, 2b, and 4b. All of these proved to be excellent precatalysts for the transfer hydrogenation of acetophenone and derivatives thereof, and cyclohexanone. With the enantiomerically pure systems 2b and 4b, only racemic products were obtained. This testifies to the hemilabile nature of the aforementioned aminophosphine ligands giving transient κ-P-bonding coordination. Since diastereoface selection of incoming substrates is based on the planar chirality of the ferrocene moiety, rather than the metal centered chirality, no enantioselective reaction takes place. |
| Формат | application.pdf |
| Издатель | Royal Society of Chemistry |
| Название | Hydrogen-transfer catalyzed by half-sandwich Ru(ii) aminophosphine complexesElectronic supplementary information (ESI) available: experimental details and NMR data for 1c and 2c. See http://www.rsc.org/suppdata/dt/b1/b104128m/ |
| Тип | research-article |
| DOI | 10.1039/b104128m |
| Electronic ISSN | 1364-5447 |
| Print ISSN | 1472-7773 |
| Журнал | Journal of the Chemical Society, Dalton Transactions |
| Первая страница | 2989 |
| Последняя страница | 2995 |
| Аффилиация | Standfest-Hauser Christina; Institute of Inorganic Chemistry, Vienna University of Technology |
| Аффилиация | Slugovc Christian; Institute of Inorganic Chemistry, Vienna University of Technology |
| Аффилиация | Mereiter Kurt; Institute of Mineralogy, Crystallography, and Structural Chemistry, Vienna University of Technology |
| Аффилиация | Schmid Roland; Institute of Inorganic Chemistry, Vienna University of Technology |
| Аффилиация | Kirchner Karl; Institute of Inorganic Chemistry, Vienna University of Technology |
| Аффилиация | Xiao Li; Institute of Organic Chemistry, University of Vienna |
| Аффилиация | Weissensteiner Walter; Institute of Organic Chemistry, University of Vienna |
| Выпуск | 20 |
| Библиографическая ссылка | A. Bader, E. Lindner, Coord. Chem. Rev., 1991, 108, 27, and references therein. |
| Библиографическая ссылка | C. Slugovc, K. Mauthner, M. Kacetl, K. Mereiter, R. Schmid, K. Kirchner, Chem. Eur. J., 1998, 4, 2043 |
| Библиографическая ссылка | C. Slugovc, P. Wiede, K. Mereiter, R. Schmid, K. Kirchner, Organometallics, 1997, 16, 2768 |
| Библиографическая ссылка | K. Mauthner, C. Slugovc, K. Mereiter, R. Schmid, K. Kirchner, Organometallics, 1997, 16, 1956 |
| Библиографическая ссылка | C. G. Arena, S. Calamia, F. Faraone, C. Graiff, A. Tiripicchio, A. J. Davenport, D. L. Davies, J. Fawcett, S. A. Garratt, D. R. Russell, J. Chem. Soc., Dalton Trans., 2000, 3149, Chem. Commun., 1999, 2331 |
| Библиографическая ссылка | F. A. Jalón, A. López-Agenjo, B. R. Manzano, M. Moreno-Lara, A. RodrÃguez, T. Sturm, W. Weissensteiner, J. Chem. Soc., Dalton Trans., 1999, 4031 |
| Библиографическая ссылка | K.-J. Haack, S. Hashiguchi, A. Fujii, T. Ikariya, R. Noyori, K.-J. Haack, S. Hashiguchi, A. Fujii, T. Ikariya, R. Noyori, Angew. Chem., 1997, 109, 297, Angew. Chem., Int. Ed. Engl., 1997, 36, 285 |
| Библиографическая ссылка | R.-X. Li, P.-M. Cheng, D.-W. Li, H. Chen, X.-J. Li, C. Wessman, N.-B. Wong, K.-Ch. Tin, J. Mol. Catal. A: Chem., 2000, 125, 179 |
| Библиографическая ссылка | P. Dani, T. Karlen, R. A. Gossage, S. Gladiali, G. van Koten, P. Dani, T. Karlen, R. A. Gossage, S. Gladiali, G. van Koten, R. Noyori, S. Hashiguchi, Angew. Chem., 2000, 112, 759, Angew. Chem., Int. Ed., 2000, 39, 743, Acc. Chem. Res., 1997, 30, 97 |
| Библиографическая ссылка | Y. Nishibayashi, I. Takei, S. Uemure, M. Hidai, Organometallics, 1999, 18, 2291 |
| Библиографическая ссылка | A. Fujii, S. Hashiguchi, N. Uematsu, T. Ikariya, R. Noyori, J. Am. Chem. Soc., 1996, 118, 2521 |
| Библиографическая ссылка | D. G. I. Petra, J. N. H. Reek, J.-W. Handgraaf, E. J. Meijer, P. Dierkes, P. C. J. Kamer, J. Brussee, H. E. Schoemaker, P. W. N. M. van Leeuwen, Chem. Eur. J., 2000, 6, 2818 |
| Библиографическая ссылка | E. Rüba, W. Simanko, K. Mauthner, K. M. Soldouzi, C. Slugovc, K. Mereiter, R. Schmid, K. Kirchner, Organometallics, 1999, 18, 3843 |
| Библиографическая ссылка | C. Slugovc, W. Simanko, K. Mereiter, R. Schmid, K. Kirchner, L. Xiao, W. Weissensteiner, Organometallics, 1999, 18, 3865 |
| Библиографическая ссылка | M. Yamakawa, H. Ito, R. Noyori, J. Am. Chem. Soc., 2000, 122, 1466 |
| Библиографическая ссылка | D. A. Alonso, P. Brandt, S. J. M. Nordin, P. G. Andersson, J. Am. Chem. Soc., 1999, 121, 9580 |
| Библиографическая ссылка | T. P. Gill, K. R. Mann, Organometallics, 1982, 1, 485 |
| Библиографическая ссылка | M. A. Bennett, A. K. Smith, J. Chem. Soc., Dalton Trans., 1974, 233 |
