1. Modulation of Metal Carbonyl Stretching Frequencies in the Second Coordination Sphere through the Internal Stark Effect
- Author
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Gemma L. Parker, Ruben Van Lommel, Nil Roig, Mercedes Alonso, Adrian B. Chaplin, Chemistry, and General Chemistry
- Subjects
DYNAMICS ,Science & Technology ,bond theory ,Chemistry, Multidisciplinary ,Organic Chemistry ,NICKEL ,Molecular Conformation ,General Chemistry ,RHODIUM ,Ligands ,electrostatic interactions ,Ruthenium ,Catalysis ,REACTIVITY ,IRIDIUM COMPLEXES ,MACROCYCLIC PNP ,ELECTRONIC-PROPERTIES ,Chemistry ,rotaxanes ,carbonyl ligands ,Physical Sciences ,Rhodium ,LIGANDS ,macrocyclic ligands ,BASIS-SETS - Abstract
Spectroscopic and computational examination of a homologous series of rhodium(I) pybox carbonyl complexes has revealed a correlation between the conformation of the flanking aryl-substituted oxazoline donors and the carbonyl stretching frequency. This relationship is also observed experimentally for octahedral rhodium(III) and ruthenium(II) variants and cannot be explained through the classical, Dewar-Chatt-Duncanson, interpretation of metal-carbonyl bonding. Instead, these findings are reconciled by local changes in the magnitude of the electric field that is projected along the metal-carbonyl vector: the internal Stark effect. ispartof: CHEMISTRY-A EUROPEAN JOURNAL vol:28 issue:69 ispartof: location:Germany status: published
- Published
- 2022