Synthesis and characterization of cationic dicarbonyl Fe(II) PNP pincer complexes

Glatz, Matthias; Schröder-Holzhacker, Christian; Bichler, Bernhard; Stöger, Berthold; Mereiter, Kurt; Veiros, Luis F.; Kirchner, Karl

doi:10.1007/s00706-016-1811-x

Record link:

https://resolver.obvsg.at/urn:nbn:at:at-ubtuw:3-1980
http://hdl.handle.net/20.500.12708/146

Title:

Synthesis and characterization of cationic dicarbonyl Fe(II) PNP pincer complexes

Citation:

Glatz, M., Schröder-Holzhacker, C., Bichler, B., Stöger, B., Mereiter, K., Veiros, L. F., & Kirchner, K. (2016). Synthesis and characterization of cationic dicarbonyl Fe(II) PNP pincer complexes. Monatshefte Für Chemie - Chemical Monthly. https://doi.org/10.1007/s00706-016-1811-x

Publisher DOI:

10.1007/s00706-016-1811-x

CatalogPlus:

AC11360172

Publication Type:

Article - Original Research Article

Language:

English

Authors:

Glatz, Matthias
Schröder-Holzhacker, Christian
Bichler, Bernhard
Stöger, Berthold
Mereiter, Kurt
Veiros, Luis F.
Kirchner, Karl

Organisational Unit:

E163 - Institut für Angewandte Synthesechemie

Journal:

Monatshefte für Chemie - Chemical Monthly

ISSN:

0026-9247

Date (published):

Oct-2016

Publisher:

Springer

Peer reviewed:

Yes

Keywords:

Iron complexes; PNP pincer ligands; Carbon monoxide; DFT calculations

Abstract:

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.

Additional information:

The final publication is available at Springer via <a href="https://doi.org/10.1007/s00706-016-1811-x" target="_blank">https://doi.org/10.1007/s00706-016-1811-x</a>.

License:

CC BY 4.0