Journal
INORGANIC CHEMISTRY
Volume 56, Issue 10, Pages 5771-5783Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.7b00393
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Funding
- Fonds der Chemischen Industrie
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Bidentate ligands containing at least one triazole or triazolylidene (mesoionic carbene, MIC) unit are,extremely popular in contemporary chemistry. One reason for their popularity is the similarities as well as differences in the donor/acceptor properties that these ligands display in comparison to their pyridine or other N-heterocyclic carbene counterparts. We present here seven rhenium(I) carbonyl complexes where the bidentate ligands contain combinations of pyricline/triazole/triazolylidene. These are the first examples of rhenium(I) complexes with bidentate 1,2,3-triazol-5-ylidene-containing ligands. All complexes were structurally characterized through H-1 and C-13, NMR spectroscopy as well as through single-crystal X-ray diffraction. A combination of structural data, redox potentials from cyclic voltammetry, and IR. data related to the CO coligands are used to gauge the donor/acceptor properties of these chelating ligands. Additionally, a combination of UV-vis-near-IR/IR/electron paramagnetic resonance spectroelectrochemistry and density functional theory calculations are used to address questions related to the electronic structures of the complexes in various redox states, their redox stability, arid the understanding of chemical reactivity following electron transfer in these systems; The results show that donor/acceptor properties in these bidentate ligands are sometimes, but not always, additive with respect;to the individual components. Additionally, these results point to, the fact that MIC-containing ligands confer remarkable redox stability to their far-Re(CO)(3)-containing metal,complexes. These findings will probably be useful for fields such as homogeneous- and electro-catalysis, photochemistry, and electrochemistry, where fac-Re(CO)(3) complexes of triazoles/triazolylidenes are likely to find use.
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