Synthesis and reactivity of BINEPINE-based chiral Fe(II) PNP pincer complexes
| Autor: | Christian Schröder-Holzhacker, Berthold Stöger, Nikolaus Gorgas, Karl Kirchner |
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| Jazyk: | angličtina |
| Předmět: |
Original Paper
Chemistry(all) 010405 organic chemistry Chemistry Hydride Ligand Iron Inorganic chemistry Diastereomer General Chemistry 010402 general chemistry 01 natural sciences Medicinal chemistry Pincer ligands 0104 chemical sciences Pincer movement Catalysis chemistry.chemical_compound Chiral phosphines Moiety Reactivity (chemistry) Carbon monoxide |
| Zdroj: | Monatshefte Fur Chemie |
| ISSN: | 0026-9247 |
| DOI: | 10.1007/s00706-016-1706-x |
| Popis: | A new asymmetric chiral PNP ligand based on the 2,6-diaminopyridine scaffold featuring a R-BINEPINE moiety was prepared. Treatment of anhydrous FeX2 (X = Cl, Br) with 1 equiv of PNP-iPr,BIN at room temperature afforded the coordinatively unsaturated paramagnetic complexes [Fe(PNP-iPr,BIN)X2]. The structure of [Fe(PNP-iPr,BIN)Cl2] is described. Both complexes react readily with the strong π-acceptor ligand CO in solution to afford selectively the diamagnetic complexes trans-[Fe(PNP-iPr,BIN)(CO)X2] in quantitative yield. Due the lability of the CO ligand, these complexes are only stable under a CO atmosphere and isolation in pure form was not possible. The preparation of the carbonyl hydride complex [Fe(PNP-iPr,BIN)(H)(CO)Br] was achieved albeit in low yields via a one pot procedure by treatment of [Fe(PNP-iPr,BINEP)Br2] with CO and subsequent reaction with Na[HBEt3]. This complex was obtained as an inseparable mixture of two diastereomers in a ca. 1:1 ratio and was tested as catalyst for the hydrogenation of ketones. The catalyst showed acceptable activity under mild conditions (5 bar H2, room temperature) with yields up to >99 % within 18 h. Graphical abstract Electronic supplementary material The online version of this article (doi:10.1007/s00706-016-1706-x) contains supplementary material, which is available to authorized users. |
| Databáze: | OpenAIRE |
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