Premium
Structure–Reactivity Relationships in the Hydrogenation of Carbon Dioxide with Ruthenium Complexes Bearing Pyridinylazolato Ligands
Author(s) -
Muller Keven,
Sun Yu,
Heimermann Andreas,
Menges Fabian,
NiednerSchatteburg Gereon,
van Wüllen Christoph,
Thiel Werner R.
Publication year - 2013
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.201204199
Subject(s) - ruthenium , acetophenone , chemistry , moiety , reactivity (psychology) , transfer hydrogenation , supercritical carbon dioxide , electronic effect , photochemistry , catalysis , medicinal chemistry , carbon dioxide , stereochemistry , organic chemistry , medicine , alternative medicine , pathology
Pyridinylazolato (N–N′) ruthenium(II) complexes of the type [(N–N′)RuCl(PMe 3 ) 3 ] have been obtained in high yields by treating the corresponding functionalised azolylpyridines with [RuCl 2 (PMe 3 ) 4 ] in the presence of a base. 15 N NMR spectroscopy was used to elucidate the electronic influence of the substituents attached to the azolyl ring. The findings are in agreement with slight differences in the bond lengths of the ruthenium complexes. Furthermore, the electronic nature of the azolate moiety modulates the catalytic activity of the ruthenium complexes in the hydrogenation of carbon dioxide under supercritical conditions and in the transfer hydrogenation of acetophenone. DFT calculations were performed to shed light on the mechanism of the hydrogenation of carbon dioxide and to clarify the impact of the electronic nature of the pyridinylazolate ligands.