Exploring the Palladium and PlatinumBis(pyridine) Complex Motif by NMR Spectroscopy, X-ray Crystallography, (Tandem) Mass Spectrometry, and Isothermal Titration Calorimetry: Do Substituent Effects Follow Chemical Intuition?

A series of ten palladiumbis(pyridine) complexes, as well as their corresponding platinum complexes, have been synthesized. The pyridine ligands in each series carried different σ-donor and/or π-acceptor/donor substituents at the para-position of their pyridine rings. These complexes were analysed b...

Full description

Saved in:
Bibliographic Details
Published in:Chemistry : a European journal 2012-12, Vol.18 (52), p.16665
Main Authors: Weilandt, Torsten, Löw, Nora L, Schnakenburg, Gregor, Daniels, Jörg, Nieger, Martin, Schalley, Christoph A, Lützen, Arne
Format: Article
Language:English
Subjects:
Chemistry
Crystallography
Enzymes
NMR
Nuclear magnetic resonance
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:A series of ten palladiumbis(pyridine) complexes, as well as their corresponding platinum complexes, have been synthesized. The pyridine ligands in each series carried different σ-donor and/or π-acceptor/donor substituents at the para-position of their pyridine rings. These complexes were analysed by NMR spectroscopy, X-ray crystallography, (tandem) MS, and isothermal titration calorimetry (ITC) to validate whether these methods allowed us to obtain a concise and systematic picture of the relative and absolute thermodynamic stabilities of the complexes, as determined by the electronic effects of the substituents. Interestingly, the NMR spectroscopic data hardly correlated with the expected substituent effects but the heteronuclear platinumphosphorus coupling constants did. Crystallographic data were found to be blurred by packing effects. Instead, tandem MS and ITC data were in line with each other and followed the expected trends. [PUBLICATION ABSTRACT]
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.201202771