title: Synthesis and characterization of cationic dicarbonyl Fe(II) PNP pincer complexes.
abstract: In the present work, we have prepared a series of octahedral Fe(II) complexes of the typetrans-[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 whethercis-[Fe(PNP)(Cl2)(CO)] ortrans-[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 oftrans-dicarbonyl Fe(II) complexes is unexpected. In fact, DFT calculations confirm thattrans-dicarbonyl complexes are indeed thermodynamically disfavored over the respectivecis-dicarbonyl compounds, but are favored for kinetic reasons.
authors.affiliation: Institute of Applied Synthetic Chemistry, Vienna University of Technology, Getreidemarkt 9/163, 1060 Vienna, Austria.
authors.forename: Mathias
authors.initials: M
authors.lastname: Glatz
authors.affiliation: Institute of Applied Synthetic Chemistry, Vienna University of Technology, Getreidemarkt 9/163, 1060 Vienna, Austria.
authors.forename: Christian
authors.initials: C
authors.lastname: Schröder-Holzhacker
authors.affiliation: Institute of Applied Synthetic Chemistry, Vienna University of Technology, Getreidemarkt 9/163, 1060 Vienna, Austria.
authors.forename: Bernhard
authors.initials: B
authors.lastname: Bichler
authors.affiliation: Institute of Chemical Technologies and Analytics, Vienna University of Technology, Getreidemarkt 9, 1060 Vienna, Austria.
authors.forename: Berthold
authors.initials: B
authors.lastname: Stöger
authors.affiliation: Institute of Chemical Technologies and Analytics, Vienna University of Technology, Getreidemarkt 9, 1060 Vienna, Austria.
authors.forename: Kurt
authors.initials: K
authors.lastname: Mereiter
authors.affiliation: Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais No. 1, 1049-001 Lisbon, Portugal.
authors.forename: Luis F
authors.initials: LF
authors.lastname: Veiros
authors.affiliation: Institute of Applied Synthetic Chemistry, Vienna University of Technology, Getreidemarkt 9/163, 1060 Vienna, Austria.
authors.forename: Karl
authors.initials: K
authors.lastname: Kirchner
keywords: Carbon monoxide; DFT calculations; Iron complexes; PNP pincer ligands