Facile C=O Bond Splitting of Carbon Dioxide Induced by Metal-Ligand Cooperativity in a Phosphinine Iron(0) Complex
| Autor: | Ruth M. Gschwind, Robert Wolf, Julia Leitl, Christian Müller, Peter Coburger, Verena Streitferdt, Michael Marquardt, Daniel J. Scott |
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| Jazyk: | angličtina |
| Rok vydání: | 2019 |
| Předmět: |
carbon dioxide fixation• iron • N
P ligands • cooperative effects• phosphinine phosphinine ddc:540 Cooperativity 010402 general chemistry Cleavage (embryo) 01 natural sciences Medicinal chemistry Catalysis Metal iron Moiety Chelation P N ligands CO2 Fixation 010405 organic chemistry Chemistry Electrophilic addition Ligand Communication Carbon fixation General Chemistry Communications 0104 chemical sciences visual_art 540 Chemie visual_art.visual_art_medium cooperative effects |
| Zdroj: | Angewandte Chemie (International Ed. in English) |
| Popis: | New iron complexes [Cp*FeL]− (1‐σ and 1‐π, Cp*=C5Me5) containing the chelating phosphinine ligand 2‐(2′‐pyridyl)‐4,6‐diphenylphosphinine (L) have been prepared, and found to undergo facile reaction with CO2 under ambient conditions. The outcome of this reaction depends on the coordination mode of the versatile ligand L. Interaction of CO2 with the isomer 1‐π, in which L binds to Fe through the phosphinine moiety in an η5 fashion, leads to the formation of 3‐π, in which CO2 has undergone electrophilic addition to the phosphinine group. In contrast, interaction with 1‐σ—in which L acts as a σ‐chelating [P,N] ligand—leads to product 3‐σ in which one C=O bond has been completely broken. Such CO2 cleavage reactions are extremely rare for late 3d metals, and this represents the first such example mediated by a single Fe centre. CO2 splitting by a single iron centre is achieved through the joint action of the metal atom and the 2‐(2′‐pyridyl)‐4,6‐diphenylphosphinine ligand (L) in the ferrate anion [Cp*FeL]− (Cp*=C5Me5). The outcome of the reaction depends on the coordination mode of L. Electrophilic addition of CO2 to the phosphinine group is observed when L is π‐coordinated, while the σ‐coordinated ligand induces C=O bond cleavage. |
| Databáze: | OpenAIRE |
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