Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 28, Issue 69, Pages -Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.202202283
Keywords
bond theory; carbonyl ligands; electrostatic interactions; macrocyclic ligands; rotaxanes
Categories
Funding
- European Research Council [637313]
- FWO Vlaanderen [1185221N, 12F4416N]
- EUTOPIA alliance
- Vrije Universiteit Brussel (VUB)
- Royal Society [UF100592, UF150675]
- Advantage West Midlands
- European Regional Development Fund
- ERC under the European Union's Horizon2020 research and innovation programme [637313]
- VUB
- Flemish Supercomputer Center (VSC)
- FWO
- Flemish Government-department EWI
- European Research Council (ERC) [637313] Funding Source: European Research Council (ERC)
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A spectroscopic and computational examination of a series of rhodium(I) pybox carbonyl complexes reveals a correlation between the conformation of the aryl-substituted oxazoline donors and the carbonyl stretching frequency. This correlation is observed in both octahedral rhodium(III) and ruthenium(II) variants and cannot be explained by the classical interpretation of metal-carbonyl bonding. Instead, it is explained by local changes in the electric field projected along the metal-carbonyl vector.
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.
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