Details
| Originalsprache | Englisch |
|---|---|
| Seiten (von - bis) | 2287-2298 |
| Seitenumfang | 12 |
| Fachzeitschrift | New Journal of Chemistry |
| Jahrgang | 35 |
| Ausgabenummer | 10 |
| Publikationsstatus | Veröffentlicht - 5 Juli 2011 |
Abstract
The syntheses, characterization, and some reactions of (phosphanylethyl) cyclopentadienyl chelate complexes of cobalt, rhodium, iridium, nickel, and chromium with unsymmetrical substitution at the phosphorus atom are described. The ligand systems were prepared by nucleophilic ring opening of spiro[2.4]hepta-4,6-diene with lithium tert-butylphenylphosphide or lithium tert-butylcyclohexylphosphide. The anionic ligands give the respective chelate complexes by treatment with metal halide reagents. In three cases it was possible to obtain X-ray crystal structure analyses. The cobalt chelate complex undergoes oxidative addition with a dihydrosilane, the reaction results in the formation of products with three stereogenic centers at phosphorus, cobalt, and silicon, which show dynamic behavior as indicated by VTNMR. The rhodium chelate complex undergoes oxidative addition of iodomethane with diastereoselective formation of the respective Rh(iii) chelate. While diastereoselectivity caused by a planar chiral indenyl ligand or by a stereogenic carbon center in the chelate backbone has earlier been observed, this is the first case of a stereoinduction by the stereogenic phosphorus ligand. Activation energies for the rotation of cobalt and rhodium chelates have also been determined by VTNMR.
ASJC Scopus Sachgebiete
- Chemische Verfahrenstechnik (insg.)
- Katalyse
- Chemie (insg.)
- Allgemeine Chemie
- Werkstoffwissenschaften (insg.)
- Werkstoffchemie
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in: New Journal of Chemistry, Jahrgang 35, Nr. 10, 05.07.2011, S. 2287-2298.
Publikation: Beitrag in Fachzeitschrift › Artikel › Forschung › Peer-Review
}
TY - JOUR
T1 - New cyclopentadienylethylphosphane chelate complexes with unsymmetrical phosphane substitution
AU - Janssen, Karin
AU - Butenschön, Holger
PY - 2011/7/5
Y1 - 2011/7/5
N2 - The syntheses, characterization, and some reactions of (phosphanylethyl) cyclopentadienyl chelate complexes of cobalt, rhodium, iridium, nickel, and chromium with unsymmetrical substitution at the phosphorus atom are described. The ligand systems were prepared by nucleophilic ring opening of spiro[2.4]hepta-4,6-diene with lithium tert-butylphenylphosphide or lithium tert-butylcyclohexylphosphide. The anionic ligands give the respective chelate complexes by treatment with metal halide reagents. In three cases it was possible to obtain X-ray crystal structure analyses. The cobalt chelate complex undergoes oxidative addition with a dihydrosilane, the reaction results in the formation of products with three stereogenic centers at phosphorus, cobalt, and silicon, which show dynamic behavior as indicated by VTNMR. The rhodium chelate complex undergoes oxidative addition of iodomethane with diastereoselective formation of the respective Rh(iii) chelate. While diastereoselectivity caused by a planar chiral indenyl ligand or by a stereogenic carbon center in the chelate backbone has earlier been observed, this is the first case of a stereoinduction by the stereogenic phosphorus ligand. Activation energies for the rotation of cobalt and rhodium chelates have also been determined by VTNMR.
AB - The syntheses, characterization, and some reactions of (phosphanylethyl) cyclopentadienyl chelate complexes of cobalt, rhodium, iridium, nickel, and chromium with unsymmetrical substitution at the phosphorus atom are described. The ligand systems were prepared by nucleophilic ring opening of spiro[2.4]hepta-4,6-diene with lithium tert-butylphenylphosphide or lithium tert-butylcyclohexylphosphide. The anionic ligands give the respective chelate complexes by treatment with metal halide reagents. In three cases it was possible to obtain X-ray crystal structure analyses. The cobalt chelate complex undergoes oxidative addition with a dihydrosilane, the reaction results in the formation of products with three stereogenic centers at phosphorus, cobalt, and silicon, which show dynamic behavior as indicated by VTNMR. The rhodium chelate complex undergoes oxidative addition of iodomethane with diastereoselective formation of the respective Rh(iii) chelate. While diastereoselectivity caused by a planar chiral indenyl ligand or by a stereogenic carbon center in the chelate backbone has earlier been observed, this is the first case of a stereoinduction by the stereogenic phosphorus ligand. Activation energies for the rotation of cobalt and rhodium chelates have also been determined by VTNMR.
UR - http://www.scopus.com/inward/record.url?scp=80053352919&partnerID=8YFLogxK
U2 - 10.1039/c1nj20292h
DO - 10.1039/c1nj20292h
M3 - Article
AN - SCOPUS:80053352919
VL - 35
SP - 2287
EP - 2298
JO - New Journal of Chemistry
JF - New Journal of Chemistry
SN - 1144-0546
IS - 10
ER -