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Title
Synthesis and characterization of cationic dicarbonyl Fe(II) PNP pincer complexes
AuthorKirchner, Karl In der Gemeinsamen Normdatei der DNB nachschlagen ; Glatz, Matthias ; Schröder-Holzhacker, Christian ; Bichler, Bernhard ; Stöger, Berthold ; Mereiter, Kurt In der Gemeinsamen Normdatei der DNB nachschlagen ; Veiros, Luis F.
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Monatshefte für Chemie - Chemical Monthly, Wien, 2016, Vol. 147, Issue 10, page 1713-1719
PublishedSpringer, 2016
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Published version
LanguageEnglish
Document typeJournal Article
Keywords (EN)Iron complexes / PNP pincer ligands / Carbon monoxide / DFT calculations
ISSN1434-4475
URNurn:nbn:at:at-ubtuw:3-1980 Persistent Identifier (URN)
DOI10.1007/s00706-016-1811-x 
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Synthesis and characterization of cationic dicarbonyl Fe(II) PNP pincer complexes [1.13 mb]
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Abstract (English)

In the present work, we have prepared a series of octahedral Fe(II) complexes of the type trans-[Fe(PNP)(CO)2Cl]+PNP are tridentate pincer-type ligands based on 2,6-diaminopyridine. These complexes are formed irrespective of the size of the substituents at the phosphorus sites and whether cis-[Fe(PNP)(Cl2)(CO)] or trans-[Fe(PNP)(Cl2)(CO)] are reacted with CO in the presence of 1 equiv of silver salts. X-ray structures of representative complexes are presented. Based on simple bonding considerations the selective formation of trans-dicarbonyl Fe(II) complexes is unexpected. In fact, DFT calculations confirm that trans-dicarbonyl complexes are indeed thermodynamically disfavored over the respective cis-dicarbonyl compounds, but are favored for kinetic reasons.

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CC-BY-License (4.0)Creative Commons Attribution 4.0 International License