Halogen-Bonded [N–I–N]− Complexes with Symmetric or Asymmetric Three-Center–Four-Electron Bonds
Yu, S., Truong, K.-N., Siepmann, M., Siiri, A., Schumacher, C., Ward, J. S., & Rissanen, K. (2023). Halogen-Bonded [N–I–N]− Complexes with Symmetric or Asymmetric Three-Center–Four-Electron Bonds. Crystal Growth and Design, 23(2), 662-669. https://doi.org/10.1021/acs.cgd.2c01162
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Crystal Growth and DesignAuthors
Date
2023Copyright
© Authors, 2023
A series of LH[Z–I–Z] halogen(I) complexes, where Z = saccharinato or phthalimido anions and LH = pyridinium, pyrazinium, tetrabutyl (TBA)- or tetramethylammonium (TMA) cations, were prepared, structurally characterized, and discussed as complexes consisting of a [N–I–N]− anion with a three-center–four-electron (3c-4e) halogen bond, and a hydrogen-bonding (pyridinium or pyrazinium) or inert (TBA or TMA) cation. The symmetric [N–I–N]− anion, reminiscent of the triiodide [I–I–I]− anion, is found to be structurally equivalent to its cationic analogue [N–I–N]+ with N–I bond lengths of 2.26 Å. In contrast to the homoleptic [N–I–N]+ complexes, asymmetry of the N–I bond lengths (2.21 and 2.28 Å) was observed for those [N–I–N]− complexes which manifested a hydrogen bond to only one saccharinato moiety, thus being structurally analogous to the asymmetric heteroleptic [N–I–N]+ complexes. The results show that the 3c-4e [N–I–N] halogen bond, being either positively or negatively charged, can be asymmetrized by an external hydrogen bond ([N–I–N]−) or by using two different ligands (heteroleptic [N–I–N]+).
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American Chemical SocietyISSN Search the Publication Forum
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https://converis.jyu.fi/converis/portal/detail/Publication/176442155
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Research Council of FinlandFunding program(s)
Academy Project, AoFAdditional information about funding
The Academy of Finland (K.R., grant no. 351121), the Magnus Ehrnrooth Foundation (J.S.W.), and the University of Jyväskylä. C.S. is grateful for a DAAD short-term grant for doctoral students and a Kekulé scholarship provided by the Verband der Chemischen Industrie e.V.License
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