Abstract: This work presents the synthesis and crystal structures of novel Ag(I) complexes based on 1,2-bis[4-chlorophenyl)imino]acenaphthene (4-Cl-C6H4-bian) and 1,2-bis[4-iodophenyl)imino]acenaphthene (4-I-C6H4-bian). The interaction of AgCF3SO3 with 4-Cl-C6H4-bian led to exclusively tetrahedral complex [Ag(4-Cl-C6H4-bian)2](CF3SO3) (1) in a 90 % yield. In contrast, the same reaction with 4-I-C6H4-bian led to the formation of both tetrahedral complex [Ag(4-I-C6H4-bian)2](CF3SO3) (2) and unexpected binuclear complex [Ag2(μ-4-I-C6H4-bian)2(4-I-C6H4-NH2)2](CF3SO3)2 (3), in which 4-I-C6H4-bian acts as a bridging ligand linking two Ag(I) ions via N- and I-donor atoms. X-ray diffraction analysis revealed an anomalously long Ag−I distance (3.0833(3) Å) in 3, resulting in duality in determining the coordination mode of the Ag(I) ion. This could be a trigonal geometry (AgN3, CN=3) or a strongly distorted trigonal-pyramidal [3+1] coordination (AgN3I, CN=4). To establish the nature of the metal–ligand interactions in complexes 1–3 and determine the coordination number of Ag(I) in complex 3, a comprehensive theoretical study (DFT calculations) was carried out using four molecular descriptors: quantum theory of atoms in molecules (QTAIM), electron localization function (ELF), interacting quantum atoms (IQA) and second-order perturbation theory analysis of the natural bond orbital (NBO).

Cite: Komlyagina V.I. , Bakaev I.V. , Romashev N.F. , Gushchin A.L.
Unusual Coordination Type of the Halogenated Bian Ligands in Silver(I) Complexes
Chemistry-an Asian Journal. 2025. Т.20. №8. e202401455 :1-10. DOI: 10.1002/asia.202401455 OpenAlex

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Published online:	Feb 14, 2025
Published print:	Apr 17, 2025

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W4407560777

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