Novel μ₅‐Coordination Modes of Aryl and Alkyl Ethynides and Classification of Metal–Ligand Interactions in Silver(I) Complexes

Abstract

Novel mu(5)-eta(1),eta(1),eta(1),eta(1),eta(2) and mu(5)-eta(1),eta(1),eta(1),eta(2),eta(2) coordination modes of alkyl and aryl ethynide moieties are found in silver(I) complexes 1-5, and the metal-ligand distances can be classified into sigma, pi and mixed (sigma,pi) types. With the consistent square-pyramidal capping Ag(5) baskets of the ethynide moiety as supramolecular synthons, a series of two- and three-dimensional coordination networks are obtained.

Diverse intermolecular interactions in silver(I)-organic frameworks constructed with flexible supramolecular synthons

“…Furthermore, utilizing new metaleligand supramolecular synthons of the type ReC^CIAg n (R ¼ aryl or alkyl; n ¼ 4, 5) [24,25] and Ag n 3C^CÀReC^CIAg n (R ¼ o-, m-, p-C 6 H 4 ; n ¼ 4, 5) [26], we have obtained a series of metaleorganic networks stabilized by argentophilic and silvereethynide (s, p and mixed s, p) interactions.…”

Molecular and Crystal Structure of Chlorido[2-(N,N,N',N'- tetramethylamidinio)ethynido]silver

“…In all cations, the C1-N bond lengths and the sum of bond angles at the nitrogen atoms have values that are compatible with a completely delocalized π bond in the amidinium (NCN) + unit. The Ag-C bond length (2.052(4)Å) is at the lower end of the range of silver-carbon σ bond lengths (2.05 -2.21Å) [10,26,33]. The bond geometry in the propiolamidinium part of silver complex 3 barely differs from that in salts 4 and 5.…”

Silver(I)-organic networks constructed with flexible silver-ethynide supramolecular synthon o-, m-, p-Cl–C6H5OCH2CC⊃Agn (n = 4, 5)

“…Furthermore, utilizing new metaleligand supramolecular synthons of the type ReC^CIAg n (R ¼ aryl or alkyl; n ¼ 4, 5) [45,46] and Ag n 3C^CÀReC^CIAg n (R ¼ o-, m-, p-C 6 H 4 ; n ¼ 4, 5) [47], we have obtained a series of metal-organic networks stabilized by argentophilic and silver-ethynide (s, p and mixed s, p) interactions. Recently, we have explored the employment of several ligands with an ethynide ethynyl group attached to a phenyl, biphenyl, or naphthyl skeleton via a flexible eCH 2 eOe link for the construction of MOFs consolidated by both silver(I)eethynide and silver(I)earomatic interactions [48e50].…”