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Base‐Initiated Formation of Fe I –PNP Pincer Complexes
Author(s) -
Glatz Mathias,
Stöger Berthold,
Bichler Bernhard,
Bauer Gerald,
Veiros Luis F.,
Pignitter Marc,
Kirchner Karl
Publication year - 2020
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201900895
Subject(s) - chemistry , pincer movement , disproportionation , cationic polymerization , deprotonation , electron paramagnetic resonance , pincer ligand , single crystal , ligand (biochemistry) , crystallography , medicinal chemistry , solvent , crystal structure , inorganic chemistry , stereochemistry , polymer chemistry , ion , catalysis , organic chemistry , nuclear magnetic resonance , biochemistry , physics , receptor
Fe(I) PNP pincer complexes of the type [Fe(PNP NH )(CO) 2 ] + were prepared by treatment of the Fe(II) complexes [Fe(PNP NH )(CO)(Cl) 2 ] with KO t Bu in an aprotic solvent. The outcome of these reactions is independent of whether it is carried out under a CO atmosphere or not. The tert ‐butyl analog [Fe(PNP NH ‐ t Bu)(CO) 2 ]Cl was obtained in a similar fashion but with [Fe(PNP NH ‐ t Bu)(Cl) 2 ] as starting material in the presence of CO. In all these reactions the formation of free PNP ligand together with unknown Fe(III) species is presumably due to a 2Fe II → Fe I and Fe III disproportionation process. The cationic complexes could be deprotonated upon treatment with KO t Bu affording the neutral complexes [Fe(PNP N )(CO) 2 ]. All compounds are low‐spin complexes as established by their solution effective magnetic moments, X‐band EPR spectra as well as DFT calculations. The solid‐state structures of two representative cationic and neutral complexes, respectively, were determined by single‐crystal X‐ray diffraction.