DOI

  • Evgeny Bulatov
  • Toni Eskelinen
  • Alexander Yu Ivanov
  • Peter M. Tolstoy
  • Elina Kalenius
  • Pipsa Hirva
  • Matti Haukka

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.

Original languageEnglish
Pages (from-to)2044-2049
Number of pages6
JournalChemPhysChem
Volume22
Issue number20
Early online date30 Jul 2021
DOIs
StatePublished - 14 Oct 2021

    Research areas

  • axial interactions, excited state, iodine, noncovalent interactions, platinum, RECOGNITION, HYDROGEN-BOND, CRYSTAL-STRUCTURE, COORDINATION, OXIDATIVE ADDITION, NICKEL(II), METAL ATOMS, TRANSITION, LIGAND, INTERMOLECULAR INTERACTIONS

    Scopus subject areas

  • Atomic and Molecular Physics, and Optics
  • Physical and Theoretical Chemistry

ID: 85604613