Synthesis, Structural Characterization, and Catalytic Activity of Indenyl Tris( N ‐pyrrolyl)phosphine Complexes of Ruthenium
| Autor: | Nigam P. Rath, Michael J. Shaw, Eike B. Bauer, Matthew J. Stark |
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| Rok vydání: | 2016 |
| Předmět: |
Steric effects
010405 organic chemistry Ligand chemistry.chemical_element Homogeneous catalysis 010402 general chemistry 01 natural sciences Toluene Medicinal chemistry 0104 chemical sciences Ruthenium Catalysis Inorganic Chemistry chemistry.chemical_compound chemistry Cyclopentadienyl complex Organic chemistry Phosphine |
| Zdroj: | European Journal of Inorganic Chemistry. 2016:1093-1102 |
| ISSN: | 1099-0682 1434-1948 |
| Popis: | The synthesis, characterization, and catalytic activity of new ruthenium complexes of the tris(N-pyrrolyl)phosphine ligand [P(pyr)3] are described. The new ruthenium complexes [RuCl(ind)(PPh3){P(pyr)3}] and [RuCl(ind){P(pyr)3}2] (ind = indenyl, η5-C9H7–) were synthesized in 73 and 63 % isolated yields, respectively, by thermal ligand exchange of [RuCl(ind)(PPh3)2] with P(pyr)3. The electronic and steric properties of the new complexes were studied through analysis of the X-ray structures and cyclic voltammetry. The new complexes [RuCl(ind)(PPh3){P(pyr)3}] and [RuCl(ind){P(pyr)3}2] and the known complex [RuCl(ind){(PPh3)2}] differed only slightly in their steric properties, as seen from the comparable bond lengths and angles around the ruthenium centers. The oxidation potentials of [RuCl(ind)(PPh3){P(pyr)3}] and [RuCl(ind){P(pyr)3}2] of +0.34 and +0.71 V versus Cp2Fe0/+ (Cp = cyclopentadienyl) are substantially higher than that of [RuCl(ind)(PPh3)2] (–0.023 V), in accordance with the enhanced π-acidity of the P(pyr)3 ligand. The new complexes are catalytically active in the etherification of propargylic alcohols and in the first ruthenium-catalyzed formation of known and new xanthenones from propargylic alcohols and diketones (18 to 72 h at 90 °C in ClCH2CH2Cl or toluene, 1–2 mol-% catalyst, 69–22 % isolated yields). |
| Databáze: | OpenAIRE |
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