Noncovalent axial I∙∙∙Pt∙∙∙I interactions in platinum(II) complexes strengthen in the excited state
Bulatov, E., Eskelinen, T., Ivanov, A. Y., Tolstoy, P. M., Kalenius, E., Hirva, P., & Haukka, M. (2021). Noncovalent axial I∙∙∙Pt∙∙∙I interactions in platinum(II) complexes strengthen in the excited state. ChemPhysChem, 22(20), 2044-2049. https://doi.org/10.1002/cphc.202100468
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ChemPhysChemAuthors
Date
2021Discipline
Orgaaninen kemiaEpäorgaaninen kemiaEpäorgaaninen ja analyyttinen kemiaAnalyyttinen kemiaOrganic ChemistryInorganic ChemistryInorganic and Analytical ChemistryAnalytical ChemistryCopyright
© 2021 The Authors. ChemPhysChem published by Wiley-VCH GmbH.
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.
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https://converis.jyu.fi/converis/portal/detail/Publication/99191669
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NMR spectra were recorded at the Center for Magnetic Resonance (St. Petersburg State University Research Park). T.E. and P.H. acknowledge grants of computer capacity from the Finnish Grid and Cloud Infrastructure (persistent identifier urn:nbn:fi:research-infras-2016072533 ).License
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