Brunner, Henri and Neuhierl, Thomas and Nuber, Bernhard (1998) Optically active transition metal complexes. Part 115. Synthesis, crystal structure and properties of chiral (eta(5)-C5H5)Ru complexes with pyrrolecarbaldiminato and salicylaldiminato ligands. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 563 (1-2). pp. 173-178. ISSN 0022-328X, 1872-8561
Full text not available from this repository.Abstract
The chiral complexes CpRu(LL*)PPh3, Cp = eta(5)-C5H5, LL*-1 = anion of 2-N-[(S)-1-phenylethyl]pyrrolecarbaldimine LL*-2 = anion of 2-N-[(R)-hydroxybut-2-yl)]pyrrolecarbaldimine (2a/2b) and LL*-3 = anion of N-[(S)-1-phenylethyl]salicylaldimine (3a/3b), can be prepared by reaction of CpRu(PPh3)(2)Cl and the corresponding ligand HLL* in boiling toluene. An X-ray structure analysis of diastereomerically pure 1a shows S-Ru configuration. The phenyl substituent of the ligand adopts a T-shape arrangement with respect to the Cp ring. The PPh3 ligand is in a right handed propeller conformation. The activation parameters of the epimerization 1a reversible arrow 1b were determined to be Delta H-not equal = (133 +/- 33) kJ mol(-1) and Delta S-not equal = (77 +/- 26) J K-1 mol(-1). The equilibrium ratios are 1a:1b = 86.14, 2a:2b = 1.1 and 3a:3b = 88:12, the attractive interaction between the Cp ring and the phenyl substituent of the chiral center in the chelating ligand LL* favoring one diastereomer of the complexes 1a/1b and 3a/3b. (C) 1998 Elsevier Science S.A. All rights reserved.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | ASYMMETRIC TRANSFER HYDROGENATION; X-RAY STRUCTURE; RUTHENIUM COMPLEXES; STEREOCHEMISTRY; ATOM; KETONES; ruthenium; chiral complexes; crystal structure |
| 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: | 23 Feb 2023 10:17 |
| Last Modified: | 23 Feb 2023 10:17 |
| URI: | https://pred.uni-regensburg.de/id/eprint/49660 |
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