Syntheses, Structures and Redox Properties of New Macrocyclic Triazatriolefinic Pd⁰ Complexes and Their Polypyrrole Modified Electrodes − Application to Heterogeneous Catalytic Suzuki Cross‐Coupling Reactions

Abstract

New triolefinic macrocyclic ligands of the type (E,E,E)-1,6,11-tris(arenesulfonyl)-1,6,11-triazacyclopentadeca-3,8,13-triene (aryl: a = ferrocenyl, b = 4-pyrrol-1-ylphenyl, c = 4-methylphenyl) and their Pd 0 complexes (1aab, 1abb and 1bcc) have been prepared and characterized. Further structural characterization in the solid state has also been performed by means of X-ray diffraction analysis for the complex 1bcc. The redox properties of both the ligands and their Pd complexes have been studied using cyclic voltammetric and coulombimetric techniques. In particular, complexes and ligands containing the pyrrole group do polymerize upon exposure to

Microwave-assisted Clauson-Kaas synthesis of pyrroles

“…When equal amounts of sulfanilamide and 1 were used, a pyrrole ring selectively formed on the aryl amino group yielding 5. 18 When two equivalents of the tetrahydrofuran were employed, condensation occurred at both ends to produce the novel dipyrrole 9.…”

Organometallic chemistry of 15-membered tri-olefinic macrocycles: catalysis by palladium(0) complexes in carbon–carbon bond-forming reactions

“…4 and Table 2). Palladium complexes 4 are obtained either by ligand-exchange using Pd(PPh 3 ) 4 or Pd(dba) 2 as sources of metal [4, 6,8,9,[11][12][13][14][15] or by in situ reduction of PdCl 2 with hydrazine in the presence of the macrocycle [10]. Excellent results are obtained with Pt(PPh 3 ) 4 to prepare platinum complexes 14, and less stable silver complexes 15 have been prepared from AgBF 4 .…”

“…Perfluorinated long chains were introduced to confer solubility of 1aff in perfluorinated solvents [7]. Complexes featuring ferrocenyl (1ggi, 1gii, 1iii, 1iip, and 1ipp), thienyl (1ggh, 1ghh) and 4-(pyrrol-1-yl)phenyl (1iip, 1ipp, and 1ggp) units have interest for electrochemical studies [9,11,12]. Vinyl-substituted 1aab has been copolymerized with styrene and divinylbenzene to afford polymer 1aac (vide infra) [6].…”

Metallocene-containing conjugated polymers

“…[369], in which both Fc (via one of its Cp ligands) and pyrrole (via nitrogen) were attached via sulfonyl groups to a macrocycle, (E,E,E)-1,6,11-tris(arenesulfonyl)-1,6,11-triazacyclopentadeca-3,8,13-triene, where three aryl groups represent either two ferrocenyl and one 4-pyrrol-1-ylphenyl 33 or versa vice. Their redox properties as well as those of their complexes with Pd(0) were studied.…”