Synthesis, catalytic activity and redox properties of palladium(0) complexes with 15-membered triolefinic macrocyclic ligands containing one, two or three ferrocenyl groups

15-Membered triolefinic macrocycles, their coordination chemistry with transition metals, and the catalytic properties of their palladium metal complexes. A review.

“…The presence of three isopropyl groups in the benzenesulfonyl moiety improves containing 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 purposes. 9,11,12 From the point of view of applications of solid supports in catalysis, 1aab has been used to prepare polymer 1aac by copolymerization with styrene and divinylbenzene (vide infra). 6 We have also prepared macrocycle 1jjj, featuring three fluorine atoms, that is a key intermediate for the synthesis of more elaborated macrocycles through aromatic nucleophilic substitution of the three fluorine atoms with phosphorus (1kkk), nitrogen (1nnn, 1ooo), and sulphur (1lll, 1mmm) nucleophiles.…”

“…Thus, complex 4ggi is also a good catalyst 9 for the Suzuki-type reaction between iodobenzene 21 and phenylboronic acid 17d (K 2 CO 3 , acetone-water 1:1, 60º) and for the Heck reaction 18 of ethyl acrylate 23 with iodobenzene 21 (KOAc, Bu 4 NBr, DMF, 60º) (Scheme 7). In both cases complex 4ggi was recovered by column chromatography on silica gel in 95 and 55% yield, respectively.…”

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 .…”

“…) [9] and the Heck reaction of ethyl acrylate 23 with iodobenzene 21 (KOAc, Bu 4 NBr, DMF, 60°C) (Scheme 7) [18]. In both cases complex 4ggi was recovered by column chromatography on silica gel in 95% and 55% yield, respectively.…”

“…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].…”