Supramolecular and Mechanochemistry of Iodine(I) Complexes: Structures and Reactivities (SMIC)
Main funder
Funder's project number: 351121
Funds granted by main funder (€)
- 599 488,00
Funding program
Project timetable
Project start date: 01/09/2022
Project end date: 31/08/2026
Summary
The project utilises still rarely used halonium ions, especially iodine(I) as very strong, yet reactive, halogen bond donors through the cationic [N-I-N]+ and neutral [N-I-N] and [O-I-N] three-center four-electron bond (3c-4e) systems to build-up new supramolecular constructs and iodination reagents (objective 1) and study their structure-reactivity relationships in some selected iodination reactions (objective 2). The use of halogen bonding in the way how it is applied in this proposal is very recently developed in the PIs laboratory under the name of Haloniumsupramolecular Chemistry, a new sub-field, much like Metallosupramolecular Chemistry is today. An iconic example of an iodine(I) complex with [N-I-N]+ 3c-4e bond, viz. an iodine(I) complex, is the bis(pyridine)iodonium(I) tetrafluoroborate, the Barluenga's reagent, which is a mild electrophilic halogenation and oxidation reagent of alkenes, alkynes and aromatics. The project builds, not so much on the now well-established [N-Ag-N]+ -> [N-I-N]+ cation exchange reaction, but on the new RCOOAg -> RCOOI-N stabilized hypoiodite and N1-I-N2 -> N1-I-N3 mechanochemical ligand-exhange reactions applied and developed very recently by the PI. These new methods to prepare new iodine(I) complexes, both supramolecular or reagents, are cost-effective and environtentally friendly. The unprecedented chemical reactivity of the supramolecular (e.g. macrocyclic) and easy to handle (stabilized hypoiodites) iodine(I) complexes have the potential to bring about new discoveries for more efficient chemical reactions and transformations. The mechanochemical synthesis of iodine(I) complexes is counter-intuitive (due to the reactivity of iodenium, viz. iodine(I), cation) but has a great potential in the design and preraration of new environmentally friendly reagents.
Principal Investigator
Other persons related to this project (JYU)
Primary responsible unit
Follow-up groups
Related publications and other outputs
- Fluoro and Trifluoromethyl Benzoyl Hypoiodite Complexes with Substituted Pyridines (2024) Kolařík, Václav; et al.; A1; OA
- Halogen bonding and mechanochemistry combined : synthesis, characterization, and application of N-iodosaccharin pyridine complexes (2024) Schumacher, Christian; et al.; A1; OA
- Modifying the terminal phenyl group of monomethine cyanine dyes as a pathway to brighter nucleic acid probes (2024) Alaranta, Johanna M.; et al.; A1; OA
- Ortho‐Substituent Effects on Halogen Bond Geometry for N‐Haloimide⋯2‐Substituted Pyridine Complexes (2024) Yu, Shilin; et al.; A1; OA
- Pyridine Iodine(I) Cations : Kinetic Trapping as a Sulfonate Complexes (2024) Puttreddy, Rakesh; et al.; A1; OA
- Chiral carbonyl hypoiodites (2023) Mattila, Milla; et al.; A1; OA
- Halogen-Bonded [N–I–N]− Complexes with Symmetric or Asymmetric Three-Center–Four-Electron Bonds (2023) Yu, Shilin; et al.; A1; OA
- Iodination of antipyrine with [N–I–N]+ and carbonyl hypoiodite iodine(i) complexes (2023) Wilson, Laura M. E.; et al.; A1; OA
- Iodine(I) and Silver(I) Complexes Incorporating 3-Substituted Pyridines (2023) Rissanen, Kari; et al.; A1; OA
- Linear bis‐Coordinate Silver(I) and Iodine(I) Complexes with R3R2R1N Tertiary Amines (2023) Kumar, Parveen; et al.; A1; OA