Details
| Originalsprache | Englisch |
|---|---|
| Seiten (von - bis) | 5212-5221 |
| Seitenumfang | 10 |
| Fachzeitschrift | Organometallics |
| Jahrgang | 28 |
| Ausgabenummer | 17 |
| Publikationsstatus | Veröffentlicht - 6 Juli 2009 |
Abstract
The synthesis of the first indenylnickel chelate complexes with a pendant phosphane ligand is described. In contrast to earlier attempts by others directed to chelates with a tethered diphenylphosphino ligand in our hands, the synthesis was successful with a di-tert-butylphosphino ligand. The anionic ligand system was generated by a nucleophilic ring-opening of spiroindene 3 with lithium di-tert-butylphosphide, a reaction that was significantly accelerated by microwave irradiation. Alternatively, the borane-protected ligand was obtained by using the lithiated borane adduct of di-tert-butylphosphane. Reaction of the anionic ligand with nickel(II) chloride gave chloro chelate 8, which was transformed to azido, cyano, and isothiocyanato complexes 9-11, the cationic acetonitrile complex 12, and representatives containing nickel-carbon bonds, including the methyl and the ethynyl derivatives 13 and 18. A crystal structure analysis of methyl chelate 13 is also included. The C NMR data of a quarternized 2-pyridylethynyl derivative 20 suggest a significant contribution of the respective allenylidene resonance formulas 21 and 22. Finally, bimetallic ferrocenylethynyl complex 23 has been included as a bimetallic representative. Some of the complexes were characterized by cyclovoltammetry.
ASJC Scopus Sachgebiete
- Chemie (insg.)
- Physikalische und Theoretische Chemie
- Chemie (insg.)
- Organische Chemie
- Chemie (insg.)
- Anorganische Chemie
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in: Organometallics, Jahrgang 28, Nr. 17, 06.07.2009, S. 5212-5221.
Publikation: Beitrag in Fachzeitschrift › Artikel › Forschung › Peer-Review
}
TY - JOUR
T1 - The first η5-indenylnickel chelate complexes with a pendant phosphane tether
AU - Hussain, Mazhar
AU - Kohser, Stefanie
AU - Janssen, Karin
AU - Wartchow, Rudolf
AU - Butenschön, Holger
PY - 2009/7/6
Y1 - 2009/7/6
N2 - The synthesis of the first indenylnickel chelate complexes with a pendant phosphane ligand is described. In contrast to earlier attempts by others directed to chelates with a tethered diphenylphosphino ligand in our hands, the synthesis was successful with a di-tert-butylphosphino ligand. The anionic ligand system was generated by a nucleophilic ring-opening of spiroindene 3 with lithium di-tert-butylphosphide, a reaction that was significantly accelerated by microwave irradiation. Alternatively, the borane-protected ligand was obtained by using the lithiated borane adduct of di-tert-butylphosphane. Reaction of the anionic ligand with nickel(II) chloride gave chloro chelate 8, which was transformed to azido, cyano, and isothiocyanato complexes 9-11, the cationic acetonitrile complex 12, and representatives containing nickel-carbon bonds, including the methyl and the ethynyl derivatives 13 and 18. A crystal structure analysis of methyl chelate 13 is also included. The C NMR data of a quarternized 2-pyridylethynyl derivative 20 suggest a significant contribution of the respective allenylidene resonance formulas 21 and 22. Finally, bimetallic ferrocenylethynyl complex 23 has been included as a bimetallic representative. Some of the complexes were characterized by cyclovoltammetry.
AB - The synthesis of the first indenylnickel chelate complexes with a pendant phosphane ligand is described. In contrast to earlier attempts by others directed to chelates with a tethered diphenylphosphino ligand in our hands, the synthesis was successful with a di-tert-butylphosphino ligand. The anionic ligand system was generated by a nucleophilic ring-opening of spiroindene 3 with lithium di-tert-butylphosphide, a reaction that was significantly accelerated by microwave irradiation. Alternatively, the borane-protected ligand was obtained by using the lithiated borane adduct of di-tert-butylphosphane. Reaction of the anionic ligand with nickel(II) chloride gave chloro chelate 8, which was transformed to azido, cyano, and isothiocyanato complexes 9-11, the cationic acetonitrile complex 12, and representatives containing nickel-carbon bonds, including the methyl and the ethynyl derivatives 13 and 18. A crystal structure analysis of methyl chelate 13 is also included. The C NMR data of a quarternized 2-pyridylethynyl derivative 20 suggest a significant contribution of the respective allenylidene resonance formulas 21 and 22. Finally, bimetallic ferrocenylethynyl complex 23 has been included as a bimetallic representative. Some of the complexes were characterized by cyclovoltammetry.
UR - http://www.scopus.com/inward/record.url?scp=69949152191&partnerID=8YFLogxK
U2 - 10.1021/om9004725
DO - 10.1021/om9004725
M3 - Article
AN - SCOPUS:69949152191
VL - 28
SP - 5212
EP - 5221
JO - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 17
ER -