Complexes of cyclen side-bridged with a methylene-bis(phosphinate) group

Pazderová, Lucia; David, Tomáš; Kotek, Jan; Kubíček, Vojtěch; Hermann, Petr

doi:10.1016/j.poly.2020.114994

Cited by 3 publications

(2 citation statements)

References 43 publications

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“…Applying molecular precursors to prepare structure-controlled catalysts with homogeneously dispersed catalytic species on the support is a well-known and widely used method. − However, there is a lack of information on applying phosphorus-containing metal complexes (phosphates, phosphonates, and phosphinates) as precursors to nonoxidative ethanol dehydrogenation catalysts. Numerous studies have been conducted on copper phosphates − and phosphonates. − However, the application of phosphinate ligands for the formation of copper complexes has seen limited exploration, with a modest number of copper complexes based on phosphinate ligands present to date. − A small amount of the copper complexes with macrocyclic ligands possessing pendant phosphinate groups are also being studied for potential medical applications. − The formation of insoluble polymeric compounds is commonplace in such systems, which is a factor that limits their potential application as molecular precursors. Typical strategies employed for the isolation of molecular species include the utilization of bulky ligands, ,…”

Section: Introductionmentioning

confidence: 99%

“… 54 − 93 A small amount of the copper complexes with macrocyclic ligands possessing pendant phosphinate groups are also being studied for potential medical applications. 94 − 101 The formation of insoluble polymeric compounds is commonplace in such systems, which is a factor that limits their potential application as molecular precursors. Typical strategies employed for the isolation of molecular species include the utilization of bulky ligands, 34 , 37 incorporation of additional ancillary ligands, 40 , 48 , 49 , 52 , 65 , 73 and the exchange of labile ligands within the molecular clusters (cluster expansion).…”

Section: Introductionmentioning

confidence: 99%

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Copper Phosphinate Complexes as Molecular Precursors for Ethanol Dehydrogenation Catalysts

Pokorny,

Doroshenko,

Machac

et al. 2023

Inorg. Chem.

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Nowadays, the production of acetaldehyde heavily relies on the petroleum industry. Developing new catalysts for the ethanol dehydrogenation process that could sustainably substitute current acetaldehyde production methods is highly desired. Among the ethanol dehydrogenation catalysts, copper-based materials have been intensively studied. Unfortunately, the Cu-based catalysts suffer from sintering and coking, which lead to rapid deactivation with time-on-stream. Phosphorus doping has been demonstrated to diminish coking in methanol dehydrogenation, fluid catalytic cracking, and ethanol-to-olefin reactions. This work reports a pioneering application of the well-characterized copper phosphinate complexes as molecular precursors for copper-based ethanol dehydrogenation catalysts enriched with phosphate groups ( Cu-phosphate/SiO 2 ). Three new catalysts ( CuP-1 , CuP-2 , and CuP-3 ), prepared by the deposition of complexes {Cu(SAAP)} n ( 1 ), [Cu 6 (BSAAP) 6 ] ( 2 ), and [Cu 3 (NAAP) 3 ] ( 3 ) on the surface of commercial SiO 2 , calcination at 500 °C, and reduction in the stream of the forming gas 5% H 2 /N 2 at 400 °C, exhibited unusual properties. First, the catalysts showed a rapid increase in catalytic activity. After reaching the maximum conversion, the catalyst started to deactivate. The unusual behavior could be explained by the presence of the phosphate phase, which made Cu 2+ reduction more difficult. The phosphorus content gradually decreased during time-on-stream, copper was reduced, and the activity increased. The deactivation of the catalyst could be related to the copper diffusion processes. The most active CuP-1 catalyst reaches a maximum of 73% ethanol conversion and over 98% acetaldehyde selectivity at 325 °C and WHSV = 2.37 h –1 .

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Copper Phosphinate Complexes as Molecular Precursors for Ethanol Dehydrogenation Catalysts

Pokorny,

Doroshenko,

Machac

et al. 2023

Inorg. Chem.

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Quinquevalent phosphorus acids

Bałczewski,

Owsianik

2024

Organophosphorus Chemistry

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This chapter shows, as in previous years, the most important achievements of the 2021 year in the area of organo-phosphorus compounds containing: three P–O bonds (Section 2: phosphoric acids and their derivatives), two P–O and one P–C bonds (Section 3: phosphonic acids and their derivatives) as well as one P–O and two P–C bonds (Section 4: phosphinic acids and their derivatives), in addition to the phosphoryl group P═O, present in all three groups of compounds. Each of the main sections covers “synthesis and reactions” including pure synthesis without applications, “synthesis and biological applications” and “synthesis and miscellaneous applications” including synthesis directed towards non-biological applications. At the end of each subsection, the corresponding achievements are shown for hetero-analogues in which phosphorus–oxygen bonds have been replaced by phosphorus–heteroatom P–X and/or P═Y bonds (X, Y = N, S or Se). The subsection on quinquevalent phosphorus acids and their derivatives as catalysts has been placed, as usual, at the end of the entire chapter, after a review of all three main groups of compounds. As in previous years, the area devoted to phosphoric and phosphonic acids and their derivatives dominated over a smaller section of phosphinic acids and their derivatives, and literature references for these sections remained at a ratio of 4 : 12 : 1. A dynamic, five-fold increase in the number of works, in the subject of chiral phosphoric acids as catalysts, has been recorded in this year.

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Recent Advances in Quinoline-Based Macrocycles: Synthesis, Properties, and Applications in Catalytic Reactions

Kumagai,

2024

Synthesis

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Macrocyclic compounds exhibit unique properties due to their large ring-shaped structures, which have captivated chemists in recent decades. These molecules exert specific functions in various applicable fields, such as chemistry, materials science, and biology. Crown ethers, calixarenes, and porphyrinoids, which contain several ether/phenol/pyrrole subunits, represent these molecular categories with unparalleled functional diversity. In contrast, quinoline-based macrocycles comprising the quinoline unit as a key element to construct specific ring shapes have received limited attention. In this minireview, we summarize the recent advances in oligoquinoline macrocycles TriQuinoline (TQ), oxa-TriQuinoline (o-TQ), TEtraQuinoline (TEQ), and other bridged quinoline-based macrocycles. Emphasis is placed on the synthesis, structure, and application of these molecules in organometallic and supramolecular chemistry, which may guide new molecular designs in the quinoline-based macrocycle family.1 Introduction2 Quinoline-Based Macrocycles2.1 TriQuinoline (TQ)2.2 Oxa-TriQuinoline (o-TQ)2.3 TEtraQuinoline (TEQ)2.4 Larger Quinoline-Based Macrocycles with Bridges3 Conclusion

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Complexes of cyclen side-bridged with a methylene-bis(phosphinate) group

Cited by 3 publications

References 43 publications

Copper Phosphinate Complexes as Molecular Precursors for Ethanol Dehydrogenation Catalysts

Copper Phosphinate Complexes as Molecular Precursors for Ethanol Dehydrogenation Catalysts

Quinquevalent phosphorus acids

Recent Advances in Quinoline-Based Macrocycles: Synthesis, Properties, and Applications in Catalytic Reactions

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