0000000001298876
AUTHOR
Marcel Siepmann
Halogen-Bonded [N–I–N]− Complexes with Symmetric or Asymmetric Three-Center–Four-Electron Bonds
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) w…
Iodine(I) and Silver(I) Complexes of Benzoimidazole and Pyridylcarbazole Derivatives
The synthesis of iodine(I) complexes with either benzoimidazole or carbazole-derived sp 2 N -containing Lewis bases is described, as well as their corresponding silver(I) complexes. The addition of elemental iodine to the linear two-coordinate Ag(I) complexes produces iodine(I) complexes with a three-center four-electron (3c-4e) [N — I — N] + bond. The 1 H and 1 H- 15 N HMBC NMR studies unambiguously confirm the formation of the complexes in all cases via the [N — Ag — N] + → [N — I — N] + cation exchange, with the 15 N NMR chemical shift change between 94 to 111 ppm when compared to the free ligand. The single crystal X-ray crystallographic studies on four I + complexes revealed highly sym…
CCDC 2106005: Experimental Crystal Structure Determination
Related Article: Essi Taipale, Marcel Siepmann, Khai-Nghi Truong, Kari Rissanen|2021|Chem.-Eur.J.|27|17412|doi:10.1002/chem.202103152
CCDC 2106359: Experimental Crystal Structure Determination
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CCDC 2106012: Experimental Crystal Structure Determination
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CCDC 2106008: Experimental Crystal Structure Determination
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CCDC 2080282: Experimental Crystal Structure Determination
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CCDC 2106021: Experimental Crystal Structure Determination
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CCDC 2106017: Experimental Crystal Structure Determination
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CCDC 2106015: Experimental Crystal Structure Determination
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CCDC 2106020: Experimental Crystal Structure Determination
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CCDC 2106013: Experimental Crystal Structure Determination
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CCDC 2106022: Experimental Crystal Structure Determination
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CCDC 2106016: Experimental Crystal Structure Determination
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CCDC 2106004: Experimental Crystal Structure Determination
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CCDC 2106007: Experimental Crystal Structure Determination
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CCDC 2106018: Experimental Crystal Structure Determination
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CCDC 2106019: Experimental Crystal Structure Determination
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CCDC 2106009: Experimental Crystal Structure Determination
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CCDC 2106362: Experimental Crystal Structure Determination
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CCDC 2106361: Experimental Crystal Structure Determination
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CCDC 2106011: Experimental Crystal Structure Determination
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CCDC 2080281: Experimental Crystal Structure Determination
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CCDC 2106003: Experimental Crystal Structure Determination
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CCDC 2106010: Experimental Crystal Structure Determination
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CCDC 2106358: Experimental Crystal Structure Determination
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CCDC 2106014: Experimental Crystal Structure Determination
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CCDC 2106006: Experimental Crystal Structure Determination
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CCDC 2106360: Experimental Crystal Structure Determination
Related Article: Essi Taipale, Marcel Siepmann, Khai-Nghi Truong, Kari Rissanen|2021|Chem.-Eur.J.|27|17412|doi:10.1002/chem.202103152