Tsuno, Takashi and Brunner, Henri and Katano, Syushi and Kinjyo, Naoto and Zabel, Manfred (2006) Synthesis of chiral-at-metal half-sandwich ruthenium(II) complexes with the CpH(PNMent) tripod ligand. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 691 (12). pp. 2739-2747. ISSN 0022-328X, 1872-8561
Full text not available from this repository. (Request a copy)Abstract
Treatment of the chiral tripod ligand (L-Ment,S-C)-CpH(PNMent) with (Ph3P)(3)RuCl2 in ethanol afforded the two chiral-at-metal diastereomers (L-Ment,S-C,R-Ru)- and (L-Ment,S-C,S-Ru)-[Cp(PNMent)Ru(PPh3)Cl] (70% de) in which the cyclopentadienyl group and the P atom of the ligand coordinated at the metal center. The (L-Ment,S-C,R-Ru)-diastereomer was isolated by crystallization from ethanol-pentane and its structure was established by X-ray crystallography. The (L-Ment,S-C,R-Ru)-diastereomer epimerized in CDCl3 solution at 60 degrees C in a first-order reaction with a half-life of 5.66 h. In alcoholic solution epimerization occurred at room temperature. Substitution of the chloride ligand in (L-Ment,S-C,R-Ru)- and (L-Ment,S-C,S-Ru)-[Cp(PNMent)Ru(PPh3)Cl] by nitriles NCR (R = Me, Ph, CH2Ph) in the presence of NH4PF6 gave mixtures of the diastereomers (L-Ment,S-C,R-Ru)- and (L-Ment,S-C,S-Ru)-[Cp(PNMent)Ru(PPh3)NCR]PF6. Treatment of (L-Ment,S-C,R-Ru)- and (L-Ment,S-C,S-Ru)-[Cp(PNMent)Ru(PPh3)Cl] with piperidine or morpholine in the presence of NH4PF6 led to the chiral-at-metal diastereomers (L-Ment,S-C,R-Ru)- and (L-Ment,S-C,S-Ru)-[Cp(PNMent)Ru(PPh3)NH3]PF6 (6% de). (c) 2006 Elsevier B.V. All rights reserved.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | CONFIGURATION; STABILIZATION; SUBSTITUTION; ruthenium; chirality; metal configuration; half-sandwich complexes; ammine complexes |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie > Alumni or Retired Professors > Prof. Dr. Henri Brunner |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 15 Feb 2021 09:52 |
| Last Modified: | 15 Feb 2021 09:52 |
| URI: | https://pred.uni-regensburg.de/id/eprint/34507 |
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