Synthesis, characterisation and reactivity of water-soluble ferrocenylimine-Rh(I) complexes as aqueous-biphasic hydroformylation catalyst precursors

Siangwata, Shepherd; Baartzes, Nadia; Makhubela, Banothile C.E.; Smith, Gregory S.

doi:10.1016/j.jorganchem.2015.04.029

Cited by 33 publications

(11 citation statements)

References 32 publications

(25 reference statements)

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“…7,8 The ferrocenyl unit is also known to modify the shapes of molecules as well as the physical properties such as colour, polarizability and magnetism. 9 Generally, studies on ferrocene revolve around generation of compounds that are used in materials science, 10 electrochemistry 11,12 catalysis, [13][14][15] medicinal applications [16][17][18][19][20][21][22][23][24] and nonlinear optics 25,26 amongst others. Ferrocene derivatives containing organic fragments bearing one or more heteroatoms such as sulphur, 27 nitrogen, 28 oxygen, 29 and phosphorous 30 have gained prominence.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, physical and antimicrobial studies of ferrocenyl-N-(pyridinylmethylene)anilines and ferrocenyl-N-(pyridinylmethyl)anilines

2016

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Section: Introductionmentioning

confidence: 99%

Synthesis, physical and antimicrobial studies of ferrocenyl-N-(pyridinylmethylene)anilines and ferrocenyl-N-(pyridinylmethyl)anilines

2016

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“…In affirmation, the mercury drop (Hg 0 ) test was conducted, where metallic mercury was added in reaction systems in separate cubes to those without (Table 4). This technique is used to establish true homogeneity of molecular catalysts from heterogeneous (nanoparticle) catalysts [64][65][66]. The results from the mercury poisoning tests are presented in Table 4 (entries 1-4; without mercury and entries 5-8; with mercury).…”

Section: Mercury Poisoning Testmentioning

confidence: 99%

Ferrocenylimine Palladium (II) Complexes: Synthesis, Characterization and Application in Mizoroki-Heck and Suzuki-Miyaura Cross-Coupling Reactions

Matsheku¹,

Tia

Maumela

et al. 2021

Catalysts

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Carbon-carbon cross-coupling reactions are essential synthetic tools for synthesizing polymers, natural products, agrochemicals, and pharmaceuticals. Therefore, new catalysts that function with greater efficiency and functional group tolerance are being researched. We have prepared new ferrocenylimine monodentate N and P donor ligands and N^N and N^P bidentate chelating ligands (L1 to L4) employed in stabilizing palladium ions for application in Mizoroki-Heck and Suzuki-Miyaura cross-coupling reactions. The ferrocenylimine ligands were successfully synthesized by Schiff base condensation reactions of acetyl ferrocene with hydrazine monohydrate to afford ferrocenyl hydrazone (L1). Ligand L1 was further treated with aldehydes to give ferrocenyl(2-diphenylphosphino)imine (L3) and ferrocenyl(pyridyl)imine (L3), while phosphination of L1 with chlorodiphenylphosphine afforded L2. The ligands were used to prepare new palladium(II) complexes (C1 to C4) by complexation with [PdCl2(MeCN)2]. All the ligands and complexes were fully characterized using standard spectroscopic and analytical techniques, including 1H NMR and 13C NMR spectroscopy, FT-IR spectroscopy, mass spectrometry and elemental analysis. The complexes (C1 to C4) were tested for efficacies in catalyzing Mizoroki-Heck and Suzuki-Miyaura C-C cross-coupling reactions and proved to be suitable catalyst precursors. Ferrocenyl(2-diphenylphosphine)imino and ferrocenyl-methyl hydrazone palladium(II) complexes C2 and C3 showed the best activities at TONs of up to 201. The ferrocenyl palladium(II) (pre)catalysts demonstrated moderate activity in Mizoroki-Heck reactions involving substrates with substituents on the olefin and aryl halide (including 4-Cl, 4-CH3, -CO2Me and -CO2Et). Density Functional Theory was used to study the mechanism of the Mizoroki-Heck cross-coupling reactions and have led to confirmation of the widely accepted catalytic cycle. Catalyst precursors (C1 to C4) also displayed good activity and selectivity in Suzuki-Miyaura cross-coupling reactions, at 0.5 mol% catalyst loading, with good tolerance to functional groups present on the aryl halide and boronic acid substrates (such as 4-Cl, 4-CHO, 4-COOH, 3-NO2, 3,5-dimethoxy and 4-CH3).

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“…The attempts to prepare water soluble complexes for biphasic catalysis find an example in the synthesis of a ferrocene substituted with sulfonato salicylaldimines to give mononuclear 5-sulfonatosalicylaldimine-ferrocenylimine Rh(I) complexes, which were then tested in the aqueous-organic biphasic hydroformylation of 1-octene, with good chemoselectivity towards aldehydes in the first cycles. The limit of these catalysts was shown by the poor conversions obtained after the fourth and fifth cycle, due to the catalyst leaching, with nearly a 90% loss of metal [70] (Figure 3).…”

Section: Cyclopentadienyl-and Ferrocenyl-based Ligandsmentioning

confidence: 99%

Rh(I) Complexes in Catalysis: A Five-Year Trend

et al. 2021

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Rhodium is one of the most used metals in catalysis both in laboratory reactions and industrial processes. Despite the extensive exploration on “classical” ligands carried out during the past decades in the field of rhodium-catalyzed reactions, such as phosphines, and other common types of ligands including N-heterocyclic carbenes, ferrocenes, cyclopentadienyl anion and pentamethylcyclopentadienyl derivatives, etc., there is still lively research activity on this topic, with considerable efforts being made toward the synthesis of new preformed rhodium catalysts that can be both efficient and selective. Although the “golden age” of homogeneous catalysis might seem over, there is still plenty of room for improvement, especially from the point of view of a more sustainable chemistry. In this review, temporally restricted to the analysis of literature during the past five years (2015–2020), the latest findings and trends in the synthesis and applications of Rh(I) complexes to catalysis will be presented. From the analysis of the most recent literature, it seems clear that rhodium-catalyzed processes still represent a stimulating challenge for the metalloorganic chemist that is far from being over.

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Synthesis, characterisation and reactivity of water-soluble ferrocenylimine-Rh(I) complexes as aqueous-biphasic hydroformylation catalyst precursors

Cited by 33 publications

References 32 publications

Synthesis, physical and antimicrobial studies of ferrocenyl-N-(pyridinylmethylene)anilines and ferrocenyl-N-(pyridinylmethyl)anilines

Synthesis, physical and antimicrobial studies of ferrocenyl-N-(pyridinylmethylene)anilines and ferrocenyl-N-(pyridinylmethyl)anilines

Ferrocenylimine Palladium (II) Complexes: Synthesis, Characterization and Application in Mizoroki-Heck and Suzuki-Miyaura Cross-Coupling Reactions

Rh(I) Complexes in Catalysis: A Five-Year Trend

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