Anion Effects on the Formation of Cross-Linked Argentophilic Interaction. Synthesis and Structural Properties of AgX Bearing Bis(3-pyridyl)dimethylsilane (X− = CF3SO3−, PF6−, and NO3−)

• Published in: Bulletin of the Chemical Society of Japan 2005-09, Vol.78 (9), p.1624-1628
• Main Authors: Park, Byung Il, Lee, Jung Woon, Lee, Young-A, Hong, Jongki, Jung, Ok-Sang
• Format: Article
• Language: English
• ISSN: 0009-2673; 1348-0634
• DOI: 10.1246/bcsj.78.1624

Anion effects on the formation of a cross-linked Ag–Ag interaction in the molecular construction of a series of AgX complexes with bis(3-pyridyl)dimethylsilane (L) (X− = CF3SO3−, PF6−, and NO3−) have been carried out. The slow diffusion of an organic solution of L into an aqueous solution of AgX afforded [Ag(L)]X or [Ag(X)(L)]. Each L connected two Ag(I) ions (Ag–N = 2.110(5)–2.161(4) Å) to form a wave strand. For CF3SO3− and PF6− anions, each single strand cross-linked the adjacent single strands via an argentophilic interaction (Ag–Ag = 3.0551(7) Å for CF3SO3−, 3.279(1) Å for PF6−) to produce unique 2D sheets. In contrast, for the NO3− anion, the anion acts as a ligand (Ag–O3N = 2.61–2.79 Å) instead of the argentophilic interaction (Ag···Ag = 3.351(1) Å). That is, a small coordinating anion is an obstacle to form the argentophilic interaction, whereas a big noncoordinating anion favors the argentophilic interaction in the present molecular construction. For all complexes, the geometry around the Ag(I) ion is a typical T-shaped arrangement. The thermal stability can be explained in terms of the structural properties, including the argentophilic interaction.