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.

Язык оригиналаанглийский
Страницы (с-по)2044-2049
Число страниц6
ЖурналChemPhysChem
Том22
Номер выпуска20
Дата раннего онлайн-доступа30 июл 2021
DOI
СостояниеОпубликовано - 14 окт 2021

    Предметные области Scopus

  • Атомная и молекулярная физика и оптика
  • Физическая и теоретическая химия

ID: 85604613