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Facile C=O Bond Splitting of Carbon Dioxide Induced by Metal–Ligand Cooperativity in a Phosphinine Iron(0) Complex
Author(s) -
Leitl Julia,
Marquardt Michael,
Coburger Peter,
Scott Daniel J.,
Streitferdt Verena,
Gschwind Ruth M.,
Müller Christian,
Wolf Robert
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201909240
Subject(s) - moiety , ligand (biochemistry) , chemistry , chelation , electrophile , metal , cooperativity , medicinal chemistry , bond cleavage , electrophilic addition , oxidative addition , stereochemistry , inorganic chemistry , catalysis , organic chemistry , biochemistry , receptor
New iron complexes [Cp*Fe L ] − ( 1‐σ and 1‐π , Cp*=C 5 Me 5 ) containing the chelating phosphinine ligand 2‐(2′‐pyridyl)‐4,6‐diphenylphosphinine ( L ) have been prepared, and found to undergo facile reaction with CO 2 under ambient conditions. The outcome of this reaction depends on the coordination mode of the versatile ligand L . Interaction of CO 2 with the isomer 1‐π , in which L binds to Fe through the phosphinine moiety in an η 5 fashion, leads to the formation of 3‐π , in which CO 2 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 CO 2 cleavage reactions are extremely rare for late 3d metals, and this represents the first such example mediated by a single Fe centre.