6533b85afe1ef96bd12b8be9
RESEARCH PRODUCT
Noncovalent axial I∙∙∙Pt∙∙∙I interactions in platinum(II) complexes strengthen in the excited state
Peter M. TolstoyToni EskelinenElina KaleniusEvgeny BulatovAlexander Yu. IvanovPipsa HirvaMatti Haukkasubject
platinakemialliset yhdisteetchemistry.chemical_elementfysikaalinen kemiaCoordination complexMetaljodinoncovalent interactionsNucleophileaxial interactionsexcited stateNon-covalent interactionsplatinumPhysical and Theoretical Chemistryexcited stateschemistry.chemical_classificationiodineCommunicationliganditAtomic and Molecular Physics and OpticsCommunicationsCrystallographychemistryCovalent bondvisual_artExcited stateIntramolecular forcevisual_art.visual_art_mediumPlatinumdescription
Abstract Coordination compounds of platinum(II) participate in various noncovalent axial interactions involving metal center. Weakly bound axial ligands can be electrophilic or nucleophilic; however, interactions with nucleophiles are compromised by electron density clashing. Consequently, simultaneous axial interaction of platinum(II) with two nucleophilic ligands is almost unprecedented. Herein, we report structural and computational study of a platinum(II) complex possessing such intramolecular noncovalent I⋅⋅⋅Pt⋅⋅⋅I interactions. Structural analysis indicates that the two iodine atoms approach the platinum(II) center in a “side‐on” fashion and act as nucleophilic ligands. According to computational studies, the interactions are dispersive, weak and anti‐cooperative in the ground electronic state, but strengthen substantially and become partially covalent and cooperative in the lowest excited state. Strengthening of I⋅⋅⋅Pt⋅⋅⋅I contacts in the excited state is also predicted for the sole previously reported complex with analogous axial interactions.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2021-08-01 |