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New amido and imido bridged complexes of copper – Syntheses and structures of [{Li(OEt2)}2][Cu(NPh2)3], [ClCuN(SnMe3)3], [{CuN(SnMe3)2}4], 1?[Cu16(NH2 tBu)12Cl16], {CuNHtBu}8]

The reactions of stannylated and lithiated amines with coppersalts (halogenides, thiocyanates) lead to amido and imido bridged complexes which contain one to twelve metal atoms. [{Li(OEt2)}2][Cu(NPh2)3] (1) results from the reaction of CuCl with LiNPh2 in the presence of trimethylphosphine. With N(SnMe3)3, CuCl reacts to the donor-acceptor complex [ClCuN(SnMe3)3] (2) that is transformed into the tetrameric complex [{CuN(SnMe3)2}4] (3) by thermolysis. 3 can also be obtained by the reaction of LiN(SnMe3)2 with Cu(SCN)2. While terminally bound in 1, the amido ligand is mu2-bridging between copper atoms in compound 3. The influence of the alkyl amide’s leaving group can be seen from a comparison of the reactivity of Me3SnNHtBu and LiNHtBu, respectively. With Me3SnNHtBu, CuCl2 forms the polymeric compound 1?[Cu16(NH2 tBu)12Cl16] (4) whereas in the case of LiNHtBu with both CuCl and CuSCN, the complex [{CuNHtBu}8] (5) is obtained. The latter contains two planar Cu4N4-rings similar to those in 3. If a mesityl group is introduced at the lithium amide, different products are accessible. Both, CuBr and CuSCN, lead to the formation of [Li(dme)3][Cu6(NHMes)3(NMes)2] (6) whose anion consists of a prismatic copper core with mu2-bridging amido and mu3-bridging imido ligands. In the presence of.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Bisamidate Prodrugs of 2-Substituted 9-[2-(Phosphonomethoxy)ethyl]adenine (PMEA, adefovir) as Selective Inhibitors of Adenylate Cyclase Toxin from Bordetella pertussis

Novel small-molecule agents to treat Bordetella pertussis infections are highly desirable, as pertussis (whooping cough) remains a serious health threat worldwide. In this study, a series of 2-substituted derivatives of 9-[2-(phosphonomethoxy)ethyl]adenine (PMEA, adefovir), in their isopropyl ester bis(L-phenylalanine) prodrug form, were designed and synthesized as potent inhibitors of adenylate cyclase toxin (ACT) isolated from B. pertussis. The series consists of PMEA analogues bearing either a linear or branched aliphatic chain or a heteroatom at the C2 position of the purine moiety. Compounds with a small C2 substituent showed high potency against ACT without cytotoxic effects as well as good selectivity over human adenylate cyclase isoforms AC1, AC2, and AC5. The most potent ACT inhibitor was found to be the bisamidate prodrug of the 2-fluoro PMEA derivative (IC50=0.145 muM). Although the bisamidate prodrugs reported herein exhibit overall lower activity than the bis(pivaloyloxymethyl) prodrug (adefovir dipivoxil), their toxicity and plasma stability profiles are superior. Furthermore, the bisamidate prodrug was shown to be more stable in plasma than in macrophage homogenate, indicating that the free phosphonate can be effectively distributed to target tissues, such as the lungs. Thus, ACT inhibitors based on acyclic nucleoside phosphonates may represent a new strategy to treat whooping cough. Whooping cough combatted: With the aim to establish a new strategy against pertussis, C2-modified adefovir analogues in their bisamidate prodrug form were found to efficiently inhibit adenylate cyclase toxin (ACT) from Bordetella pertussis. The compounds show favorable plasma stability, effective distribution to target tissues, and good selectivity for ACT over human adenylate cyclase isoforms.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

Final Thoughts on Chemistry for Copper(I) oxide

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Perfluoroalkylsulfonamidoaryl compounds

Phenyl-substituted perfluoroalkanesulfonanilides in which the phenyl rings are linked by sulfur, sulfinyl or sulfonyl and salts thereof in which the rings and the perfluoroalkylsulfonamido nitrogen are optionally substituted. The compounds are active herbicides and some are anti-inflammatory agents and analgesic agents.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

Brief introduction of Cuprous thiocyanate

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Synthesis, Crystal Structure and Chemical Reactivity of Dichloro(thiosemicarbazide)copper(II)

The structure of dichloro(thiosemicarbazide)copper(II), , has been determined by X-ray crystallography.Contrary to earlier proposals the compound is found to be monomeric.Electron spin resonance studies of the compound both as a polycrystalline solid and in dimethylformamide solution are also in accordance with a monomeric structure.The reactivity of towards some Lewis bases such as imidazole, 2,2′-bipyridyl etc. has also been studied.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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High- k Gate Dielectrics for Emerging Flexible and Stretchable Electronics

Recent advances in flexible and stretchable electronics (FSE), a technology diverging from the conventional rigid silicon technology, have stimulated fundamental scientific and technological research efforts. FSE aims at enabling disruptive applications such as flexible displays, wearable sensors, printed RFID tags on packaging, electronics on skin/organs, and Internet-of-things as well as possibly reducing the cost of electronic device fabrication. Thus, the key materials components of electronics, the semiconductor, the dielectric, and the conductor as well as the passive (substrate, planarization, passivation, and encapsulation layers) must exhibit electrical performance and mechanical properties compatible with FSE components and products. In this review, we summarize and analyze recent advances in materials concepts as well as in thin-film fabrication techniques for high-k (or high-capacitance) gate dielectrics when integrated with FSE-compatible semiconductors such as organics, metal oxides, quantum dot arrays, carbon nanotubes, graphene, and other 2D semiconductors. Since thin-film transistors (TFTs) are the key enablers of FSE devices, we discuss TFT structures and operation mechanisms after a discussion on the needs and general requirements of gate dielectrics. Also, the advantages of high-k dielectrics over low-k ones in TFT applications were elaborated. Next, after presenting the design and properties of high-k polymers and inorganic, electrolyte, and hybrid dielectric families, we focus on the most important fabrication methodologies for their deposition as TFT gate dielectric thin films. Furthermore, we provide a detailed summary of recent progress in performance of FSE TFTs based on these high-k dielectrics, focusing primarily on emerging semiconductor types. Finally, we conclude with an outlook and challenges section.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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3-Aryluracils having an ether (thio) carbomyloxy or sulphomyloxy substituent on the aromatic moiety

The invention is concerned with 3-aryluracils of the formula STR1 wherein R1, R2, R3, R4, R5 and R6 are as described herein, as well as salts thereof and their manufacture, weed control compositions which contain such compounds as the active substance and the use of the active substances or compositions for weed control. The invention is also concerned with herbicidally-active starting materials and weed control compositions containing these.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Extending motifs in lithiocuprate chemistry: Unexpected structural diversity in thiocyanate complexes

The new area of lithio(thiocyanato)cuprates has been developed. Using inexpensive, stable and safe CuSCN for their preparation, these complexes revealed Lipshutz-type dimeric motifs with solvent-dependent point group identities; planar, boat-shaped and chair shaped conformers are seen in the solid state. In solution, both Lipshutz-type and Gilman structures are clearly seen. Since the advent in 2007 of directed ortho cupration, effort has gone into understanding the structure-reactivity effects of amide ligand variation in and alkali metal salt abstraction from Lipshutz-type cuprates such as (TMP)2Cu(CN)Li2(THF) 1 (TMP = 2,2,6,6-tetramethylpiperidide). The replacement of CN- with SCN- is investigated presently as a means of improving the safety of lithium cuprates. The synthesis and solid state structural characterization of reference cuprate (TMP)2Cu(CN)Li2(THP) 8 (THP = tetrahydropyran) precedes that of the thiocyanate series (TMP)2Cu(SCN)Li2(L) (L = OEt29, THF 10, THP 11). For each of 9-11, preformed TMPLi was combined with CuSCN (2 : 1) in the presence of sub-stoichiometric Lewis base (0.5 eq. wrt Li). The avoidance of Lewis basic solvents incurs formation of the unsolvated Gilman cuprate (TMP)2CuLi 12, whilst multidimensional NMR spectroscopy has evidenced the abstraction of LiSCN from 9-11 in hydrocarbon solution and the in situ formation of Gilman reagents. The synthetic utility of 10 is established in the selective deprotometalation of chloropyridine substrates, including effecting transition metal-free homocoupling in 51-69% yield.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Electronic Modulation of Electrocatalytically Active Center of Cu7S4 Nanodisks by Cobalt-Doping for Highly Efficient Oxygen Evolution Reaction

Cu-based electrocatalysts have seldom been studied for water oxidation because of their inferior activity and poor stability regardless of their low cost and environmentally benign nature. Therefore, exploring an efficient way to improve the activity of Cu-based electrocatalysts is very important for their practical application. Modifying electronic structure of the electrocatalytically active center of electrocatalysts by metal doping to favor the electron transfer between catalyst active sites and electrode is an important approach to optimize hydrogen and oxygen species adsorption energy, thus leading to the enhanced intrinsic electrocatalytic activity. Herein, Co-doped Cu7S4 nanodisks were synthesized and investigated as highly efficient electrocatalyst for oxygen evolution reaction (OER) due to the optimized electronic structure of the active center. Density-functional theory (DFT) calculations reveal that Co-engineered Cu7S4 could accelerate electron transfer between Co and Cu sites, thus decrease the energy barriers of intermediates and products during OER, which are crucial for enhanced catalytic properties. As expected, Co-engineered Cu7S4 nanodisks exhibit a low overpotential of 270 mV to achieve current density of 10 mA cm-2 as well as decreased Tafel slope and enhanced turnover frequencies as compared to bare Cu7S4. This discovery not only provides low-cost and efficient Cu-based electrocatalyst by Co doping, but also exhibits an in-depth insight into the mechanism of the enhanced OER properties.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Triazapentadienes as acaricides

Certain heteroaryl triazapentadienes with acaricidal properties and their preparation are described.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Two novel cation-induced supramolecular polymers with 2-3D polymeric cuprous thiocyanate frameworks: Synthesis, characterization and photocatalytic activities for the degradation of organic dye contaminants

In order to systematically explore the photocatalytic activity of the inorganic-organic supramolecular polymers induced by 1,1?-(1,n-alkylidene)bis[4-methylpyridinium] (n = 1-2) cations, two novel cation-induced compounds, {(bmpm) [Cu2(SCN)4]}n (bmpm = 1,1?-methylenebis[4-methylpyridinium] (1) and {(bmpe) [Cu2(SCN)4]}n (bmpe = 1,1?-(1,2-ethanediyl)bis[4-methylpyridinium] (2) were obtained and characterized by X-ray crystallography. Compound 1 has a 3D framework with the cations trapped within host network cavities. Compound 2 possesses an infinite 2D supramolecular polypseudorotaxane structure linked by bridging thiocyanate groups. The third-order NLO, optical band gaps and photocatalytic activities of 1 and 2 were also evaluated. Remarkably, both 1 and 2 exhibited good photocatalytic abilities.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”