期刊
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
卷 -, 期 20, 页码 3320-3330出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/ejic.201200369
关键词
Isomerization; Allylic compounds; Iridium; Structure-activity relationships; N ligands
资金
- Swiss National Foundation [200020_132681]
- State Secretariat for Education and Research
- Roche
- Swiss National Science Foundation (SNF) [200020_132681] Funding Source: Swiss National Science Foundation (SNF)
The evaluation of a series of cationic iridium complexes in the isomerization of primary allylic alcohols has revealed the unique ability of Crabtree catalysts [(Cy3P)(C6H5N)Ir(cod)]center dot X 1a (X = PF6) and 1b (X = BArF; cod = 1,5-cyclooctadiene) to catalyze efficiently this transformation. Emphasis has been placed on understanding the electronic factors that govern the catalytic process by using a range of para-substituted pyridine N-donor ligands. Excellent correlations between analytical data (13C NMR chemical shift; ?CO) and established thermodynamic and kinetic parameters (pKa, Mayr nucleophilicity parameter N) have been elaborated. Overall, the results obtained point to the possibility of qualitatively predicting the activity of Crabtree catalyst analogues in the isomerization of primary allylic alcohols.
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