3,11,19‐Trithia[3.3.3]pyridinophane: Structural Diversity in Its Transition Metal Complexes

Abstract

The pyridine-containing aza-thia macrocycle 3,11,19-trithia-[3.3.3]pyridinophane (10) IntroductionCrystal engineering remains one of the most fascinating areas of research in modern inorganic chemistry. It has given rise to many remarkable structures by using transition metals through the development of coordination polymers, the construction of molecular architectures and the self-assembly of complex molecular structures.[1Ϫ12] The coordination chemistry of pyridine-containing macrocycles is of particular interest due to the effective coordination ability of pyridine.[13] Parallel to this, binuclear macrocyclic complexes have also attracted much attention as catalysts and models for certain metalloenzymes. [14,15] There is also a need to understand the nature and extent of metal-metal interactions. Schröder et al.[16Ϫ18] and others [19Ϫ22] have reported a series of coordination polymers derived from Ag I and thioether macrocycles 1Ϫ5 as well as other functionalised thioether macrocycles. [23,24] The search for appropriate organic building blocks for the construction of coordination polymers and the study of binuclear complexes led us to investigate the ligand 10. The intramolecular layout of the three pyridine rings in 10 means that it is able to form a cone-like conformation similar to that of calixarenes and thus 10 was expected to exhibit interesting complexation properties.We report herein a new synthetic route to the macrocycle 10 and the preparation of a series of its transition metal [a]

Synthesis, Stability Constant Determination, and Structural Study of Some Complexes of a Zinc Triad Containing Pyridyl‐amine‐quinoline and Pyridyl‐thio‐quinoline

“…(2)], again within the experimental range, and are similar to those found in the cation reported in ref. [25] (2.363, 2.401 Å) and in the neutral complexes reported in ref. [26] (2.373, 2.400 Å) and ref.…”

“…[27] It is worth noting that complexes in which a five-coordinate Hg II is surrounded at the same time by pyridyl and thioether ligands are rather uncommon. [22,25] Recently, Bebout and co-workers [14] described some zinc triad complexes (with c.n. = 4, 5, or 6) of a symmetric N,S mixed ligand (L) closely related to NSN(Qui [14] Search (c) returned about 20 entries, but only 11 of these show an aliphatic amine donor atom like 3.…”

Synthesis and structural analysis of polynuclear silver(I) complexes with 4,7-phenanthroline

“…[8][9][10][11][12][13][14] The Ag1-N3 (acetonitrile) bond distance of 2.284 (7) Å falls in the normal range of 2.18-2.33 Å. 26 On the other hand, the Ag1-O1 bond distance of 2.505(6) Å is much longer than usual covalent silver(I)-oxygen bonds of approximately 2.3 Å. 8 In complex 1, two Ag(I) ions are connected by one 4,7-phen, which behaves as a bridging ligand.…”

Fluxional interconversion of divalent palladium complexes having NSNSN ligands between flexible SNS and rigid NNN-coordinated structures

“…Such work has focused on the behaviors of the complexes [8][9][10][11][12][13][14][15][16][17] as well as the influences of the ligand hemilability on fundamental reactions, such as insertion of unsaturated compounds into Pd-C bonds, [18][19][20][21][22][23][24] attack of nitrogen nucleophiles to  3 -allyl complexes, [25][26][27][28] and catalytic reactions such as the Mizoroki-Heck reaction 29,30 and allylic substitution. 31 Structurally distinctive Pd-SNS complexes with macrocyclic architectures, [32][33][34][35] dendrimer 36, 37 -or carborane 38 -incorporated Pd-SNS complexes, as well as the Pd-SN complexes with cysteine-derived ligands 39 have been also reported. On the other hand, transition-metal complexes having available, free basic moieties adjacent to the metal center are also intriguing.…”