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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?
Author(s) -
Weilandt Torsten,
Löw Nora L.,
Schnakenburg Gregor,
Daniels Jörg,
Nieger Martin,
Schalley Christoph A.,
Lützen Arne
Publication year - 2012
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201202771
Subject(s) - chemistry , substituent , isothermal titration calorimetry , pyridine , palladium , heteronuclear molecule , crystallography , nuclear magnetic resonance spectroscopy , platinum , stereochemistry , medicinal chemistry , organic chemistry , catalysis
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.