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Attractive models: Synthetic ZnII complexes were investigated as models of copper-zinc superoxide dismutase. Superoxide underwent a unique disproportionation reaction in the electrostatic sphere of the complexes (see picture; bpy=2,2?-bipyridyl). The effectiveness of the ZnII complexes in inducing the disproportionation of superoxide depended on both the Lewis acidity and the coordination geometry of the Zn center. Copyright

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Metal catalyst and ligand design,
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Divalent cobalt and iron chloride complexes of the type [LMCl 2]n (n = 1 or 2), [LMCl]Cl, [LMCl]2[MCl 4] and [L2M]Cl2 are accessible on treatment of L [L = bis (2-pyridylmethyl)amine (DPA) and tris(2-pyridylmethyl)amine (TPA)] with anhydrous MCl2 in n-BuOH at elevated temperatures; complex [(DPA)FeCl2]2 undergoes oxidation in air to give the oxo-bridged species, [{(DPA)FeCl2}2(mu-O)]. All the complexes have been spectroscopically and structurally characterised. Treatment of {(2-C5H4N)CH2}3N (TPA) with one equivalent of MCl2 in n-BuOH at elevated temperatures affords the six-coordinate complexes [(TPA)MCl2] (M = Co (1), Fe (2)) and, in the case of CoCl2, the five-coordinate chloride salt [(TPA)CoCl]Cl (3). Conversely, addition of an excess of CoCl2 in the latter reaction leads to [(TPA)CoCl]2[CoCl4] (4) as the only isolable product. Interaction of one equivalent of {(2-C5H4N) CH2}2NH (DPA) and MCl2 under similar reaction conditions to that described above affords the dimeric species [(fac-DPA)MCl(mu-Cl)]2 (M = Co (5), Fe (6)), while the bis(ligand) halide salts [(fac-DPA)2M]Cl2 (M = Co (7), Fe (8)) are accessible on addition of two equivalents of DPA. In the presence of air, 6 undergoes oxidation to give [{(fac-DPA)FeCl2}2(mu-O)] (9). Single-crystal X-ray diffraction studies are reported for 1, 2 ? MeCN, 3, 6·123CH2Cl2, 7 ? 3MeCN, 8 ? 3MeCN and 9.

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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A catalyst don’t appear in the overall stoichiometry of the reaction it catalyzes, COA of Formula: C18H18N4, but it must appear in at least one of the elementary reactions in the mechanism for the catalyzed reaction. 16858-01-8, Name is Tris(2-pyridylmethyl)amine, molecular formula is C18H18N4. In a Article, authors is Kaur, Amandeep,once mentioned of 16858-01-8

ConspectusThe availability of electrons to biological systems underpins the mitochondrial electron transport chain (ETC) that powers living cells. It is little wonder, therefore, that the sufficiency of electron supply is critical to cellular health. Considering mitochondrial redox activity alone, a lack of oxygen (hypoxia) leads to impaired production of adenosine triphosphate (ATP), the major energy currency of the cell, whereas excess oxygen (hyperoxia) is associated with elevated production of reactive oxygen species (ROS) from the interaction of oxygen with electrons that have leaked from the ETC. Furthermore, the redox proteome, which describes the reversible and irreversible redox modifications of proteins, controls many aspects of biological structure and function. Indeed, many major diseases, including cancer and diabetes, are now termed “redox diseases”, spurring much interest in the measurement and monitoring of redox states and redox-active species within biological systems.In this Account, we describe recent efforts to develop magnetic resonance (MR) and fluorescence imaging probes for studying redox biology. These two classes of molecular imaging tools have proved to be invaluable in supplementing the structural information that is traditionally provided by MRI and fluorescence microscopy, respectively, with highly sensitive chemical information. Importantly, the study of biological redox processes requires sensors that operate at biologically relevant reduction potentials, which can be achieved by the use of bioinspired redox-sensitive groups. Since oxidation-reduction reactions are so crucial to modulating cellular function and yet also have the potential to damage cellular structures, biological systems have developed highly sophisticated ways to regulate and sense redox changes. There is therefore a plethora of diverse chemical structures in cells with biologically relevant reduction potentials, from transition metals to organic molecules to proteins. These chemical groups can be harnessed in the development of exogenous molecular imaging agents that are well-tuned to biological redox events.To date, small-molecule redox-sensitive tools for oxidative stress and hypoxia have been inspired from four classes of cellular regulators. The redox-sensitive groups found in redox cofactors, such as flavins and nicotinamides, can be used as reversible switches in both fluorescent and MR probes. Enzyme substrates that undergo redox processing within the cell can be modified to provide fluorescence or MR readout while maintaining their selectivity. Redox-active first-row transition metals are central to biological homeostasis, and their marked electronic and magnetic changes upon oxidation/reduction have been used to develop MR sensors. Finally, redox-sensitive amino acids, particularly cysteine, can be utilized in both fluorescent and MR sensors.

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Chemistry is traditionally divided into organic and inorganic chemistry. Recommanded Product: Tris(2-pyridylmethyl)amine. The former is the study of compounds containing at least one carbon-hydrogen bonds.In a patent,Which mentioned a new discovery about 16858-01-8

Thermosensitive injectable hydrogels have been used for the delivery of pharmacological and cellular therapies in a variety of soft tissue applications. A promising class of synthetic, injectable hydrogels based upon oligo(ethylene glycol) methacrylate (OEGMA) monomers has been previously reported, but these polymers lack reactive groups for covalent attachment of therapeutic molecules. In this work, thermosensitive, amine-reactive and amine-functionalized polymers were developed by incorporation of methacrylic acid N-hydroxysuccinimide ester or 2-aminoethyl methacrylate into OEGMA-based polymers. A model therapeutic peptide, bivalirudin, was conjugated to the amine-reactive hydrogel to investigate effects on the polymer thermosensitivity and gelation properties. The ability to tune the thermosensitivity of the polymer in order to compensate for peptide hydrophilicity and maintain gelation capability below physiological temperature was demonstrated. Cell encapsulation studies using an H9 T-cell line (CD4+) were conducted to evaluate feasibility of the hydrogel as a carrier for cellular therapies. Although this class of polymers is generally considered to be non-toxic, it was found that concentrations required for gelation were incompatible with cell survival. Investigation into the cause of cytotoxicity revealed that a hydrolysis byproduct, diethylene glycol monomethyl ether, is likely a contributing factor. While modifications to structure or composition will be required to enable viable cell encapsulation, the functionalized injectable hydrogel has the potential for controlled delivery of a wide range of drugs.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Chemistry is the experimental and theoretical study of materials on their properties at both the macroscopic and microscopic levels.In a patent, Safety of Tris(2-pyridylmethyl)amine, Which mentioned a new discovery about 16858-01-8

Dinuclear [(TPyA)FeII(THBQ2-)FeII(TPyA)] (BF4)2 (1) possesses hydrogen bonding interactions that form a 1-D chain, and pi-pi interactions between the 1-D chains that give rise to a 2-D supramolecular-layered structure, inducing hysteresis in the spin crossover behavior; 1 has shown spin crossover behavior around 250 K with thermal hysteresis and ferromagnetic interactions at low temperature. The Royal Society of Chemistry.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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An oxo-bridged dirhenium(III,III) complex of tris(2-pyridylmethyl)amine (tpa) and its one-electron oxidized (III,IV) species, [Re2(mu-O)Cl2(tpa)2]3+,4+ have been prepared. They are new members to a series of rhenium tpa complexes in various oxidation states. X-ray structural determination of the Re2(III,IV) complex revealed practically linear Re-O-Re bridge (178(1)) with short Re-O distances of 1.85(2) A? indicative of some multiple bonded character. The 1H NMR spectrum disclosed the relatively slow rotation around the Re-O-Re axis in CH3CN solution in the timescale of 1H NMR. The complex undergoes two consecutive reversible one electron oxidations Re2(III,III)/(III,IV) and Re2(III,IV)/(IV,IV) at E1/2=0.23 and 0.90 V vs Ag/AgCl, respectively. Strong visible absorption bands are observed for the Re2(III,III) species at 448 (epsilon=31 160) and 563 nm (19 550) which are tentatively assigned to MLCT transitions. A unique oxidation product, Re2(mu-O)(O)2Cl2(bpaO2) 2 (bpaO2H=1,3-bis(2-pyridyl)-2-aza-propanedione) has also been isolated and its crystal structure was determined. The complex is dirhenium(V) species with linear O=Re-O-Re=O moiety. Ligand tpa has been oxidized to ketone with simultaneous dissociation of one of the 2-pyridylmethyl arms.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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The complex ReIII(benzil)(PPh3)Cl3 (2) is used to synthesize a variety of ReIII and ReII polypyridyl complexes of the type cis-[ReIII(L2)2Cl2]+, [ReII(L2)3]2+, ReIII(L3)Cl3, [ReIII(L3)2Cl]2+, and [ReIII(L4)Cl2]+, where L2 = bpy (3 and 6), tbpy (4 and 7), phen (5 and 8); L3 = terpy (9 and 10); L4 = TMPA (11). The complex cis-[ReIII(bpy)2Cl2]+ (3) is a useful synthon in the formation of complexes of the type [Re(bpy)2Lx]n+ that are six- or seven-coordinate ReIII complexes (13, 16, and 18) or octahedral ReII or ReI complexes (12 and 17). The [ReIII(terpy)2Cl]2+ (10) complex can be reduced to form the ReI complex, [ReI(terpy)2]+ (21) and then electrochemically reoxidized to form new complexes of the type [ReIII(terpy)2L]n+. Similar behavior is observed for the [ReII(bpy)3]2+ (6) complex where [ReIII(bpy)3(1BuNC)3+ (20) and [ReI(bpy)3]+ (19) may be formed. The electrochemistry of these complexes is discussed in relation to their reactivity and the observed pi-acidity of the polypyridyl ligands. In addition, X-ray crystal structures for cis-[ReIII(bpy)2Cl2]PF6 (3) and [ReI(bpy)3]PF6 (19) are reported. cis-[ReIII(bpy)2Cl2]PF6 (3, ReC20H16N4Cl2F6P) crystallizes in the monoclinic space group C2/c with Z = 4 and lattice parameters a = 15.043(5) A, b = 13.261(4) A, c = 12.440(4) A, and beta= 108.86(2) at -100 C. [ReI(bpy)3]PF6 (19, ReC30H24N6F6P) crystallizes in the rhombohedral space group R3c(h) (No. 167) with Z = 12 and lattice parameters a = 13.793(3) Aand c = 51.44(3) A at -100 C.

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Carbon monoxide readily binds to heme and copper proteins, acting as a competitive inhibitor of dioxygen. As such, CO serves as a probe of protein metal active sites. In our ongoing efforts to mimic the active site of cytochrome c oxidase, reactivity toward carbon monoxide offers a unique opportunity to gain insight into the binding and spectroscopic characteristics of synthetic model compounds. In this paper, we report the synthesis and characterization of CO-adducts of (5/6L)FeII, [(5/6L)FeII…CuI](B (C6F5)4), and [(TMPA)CuI(CH3CN)](B(C6 F5)4), where TMPA = tris(2-pyridylmethyl)amine and 5/6L = a tetraarylporphyrinate tethered in either the 5-position (5L) or 6-position (6L) to a TMPA copper binding moiety, Reaction of (5/6L)FeII {in THF (293 K): UV-vis 424 (Soret), 543-544 nm; 1H NMR deltapyrrole 52-59 ppm (4 peaks); 2H NMR (from (5L-d8)FeII) deltapyrroole 53.3, 54.5, 55.8, 56.4 ppm} with CO in solution at RT yielded (5/6L)FeII-CO {in THF (293 K): UV-vis 413-414 (Soret), 532-533 nm; IR v(CO)Fe 1976-1978 cm-1; 1H NMR deltapyrrole 8.8 ppm; 2H NMR (from (5L-d8)FeII-CO) deltapyrrole 8.9 ppm; 13C NMR delta(CO)Fe 206.8-207.1 ppm (2 peaks)}. Experiments repeated in acetonitrile, acetone, toluene, and dichloromethane showed similar spectroscopic data. Binding of CO resulted in a change from five-coordinate, high-spin Fe(II) to six-coordinate, low-spin Fe(II), as evidenced by the upfield shift of the pyrrole resonances to the diamagnetic region (1H and 2H NMR spectra), Addition of CO to [(5/6L)FeII…CuI](B (C6F5)4) {in THF (293 K): UV-vis (6L only) 424 (Soret), 546 nm; 1H NMR deltapyrrole 54-59 ppm (multiple peaks); 2H NMR (from [(5L-d8)FeII…CuI (B(C6F5)4)) deltapyrrole 53.4 ppm (br)} gave the bis-carbonyl adduct [(5/6L)FeIICO…CuI-CO](B (C6F5)4) {in THF (293 K): UV-vis (6L only) 413 (Soret), 532 nm; IR v(CO)Fe 1971-1973 cm-1, v(CO)Cu 2091-2093 cm-1, ?2070(sh) cm-1; 1H NMR deltapyrole 8.7-8.9 ppm; 2H NMR (from [(5L-d8)FeII·· ·CuICO](B(C6F5)4)) deltapyrole 8.9 ppm; 13C NMR delta(CO)Fe 206.8-208.1 ppm (2 peaks), deltaCO)Cu 172.4 (5L), 178,2 (6L) ppm}. Experiments in acetonitrile, acetone, and toluene exhibited spectral features similar to those reported, The [(5/6L)FeII-CO··· CuICO](B(C6F5)4) compounds yielded (CO)Fe spectra analogous to those seen for (5/6L)FeII-CO and (CO)Cu, spectra similar to those seen for [(TMPA)CuICO](B(C6F5)4) {in THF (293 K): IR v(CO)Cu, 2091 cm-1, ?2070(sh) cm-1; 13C NMR delta(CO)Cu 180.3 ppm}. Additional IR studies were performed in which the [5L)FeII-CO···CuI-CO] (B(C6F5)4) in solution was bubbled with argon in an attempt to generate the iron-only mono-carbonyl [5L)FeII-CO···Cu] (B(C6F5)4) species; in coordinating solvent or with axial base present, decreases in characteristic IR-band intensities revealed complete loss of CO from copper and variable loss of CO from the heme.

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Chemistry is the experimental and theoretical study of materials on their properties at both the macroscopic and microscopic levels.In a patent, Quality Control of: Tris(2-pyridylmethyl)amine, Which mentioned a new discovery about 16858-01-8

Three mononuclear cobalt(ii)-carboxylate complexes, [(TPA)CoII(benzilate)]+ (1), [(TPA)CoII(benzoate)]+ (2) and [(iso-BPMEN)CoII(benzoate)]+ (3), of N4 ligands (TPA = tris(2-pyridylmethyl)amine and iso-BPMEN = N1,N1-dimethyl-N2,N2-bis((pyridin-2-yl)methyl)ethane-1,2-diamine) were isolated to investigate their reactivity toward dioxygen. Monodentate (eta1) binding of the carboxylates to the metal centre favours the five-coordinate cobalt(ii) complexes (1-3) for dioxygen activation. Complex 1 slowly reacts with dioxygen to enable the oxidative decarboxylation of the coordinated alpha-hydroxy acid (benzilate). Prolonged exposure of the reaction solution of 2 to dioxygen results in the formation of [(DPA)CoIII(picolinate)(benzoate)]+ (4) and [CoIII(BPCA)2]+ (5) (DPA = di(2-picolyl)amine and HBPCA = bis(2-pyridylcarbonyl)amide), whereas only [(DPEA)CoIII(picolinate)(benzoate)]+ (6) (DPEA = N1,N1-dimethyl-N2-(pyridine-2-ylmethyl)-ethane-1,2-diamine) is isolated from the final oxidised solution of 3. The modified ligand DPA (or DPEA) is formed via the oxidative C-N bond cleavage of the supporting ligands. Further oxidation of the -CH2- moiety to -C(O)- takes place in the transformation of DPA to HBPCA on the cobalt(ii) centre. Labelling experiments with 18O2 confirm the incorporation of oxygen atoms from molecular oxygen into the oxidised products. Mixed labelling studies with 16O2 and H2O18 strongly support the involvement of water in the C-N bond cleavage pathway. A comparison of the dioxygen reactivity of the cobalt complexes (1-3) with those of several other five-coordinate mononuclear complexes [(TPA)CoII(X)]+/2+ (X = Cl, CH3CN, acetate, benzoylformate, salicylate and phenylpyruvate) establishes the role of the carboxylate co-ligands in the activation of dioxygen and subsequent oxidative cleavage of the supporting ligands by a metal-oxygen oxidant.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Rh-containing metallacycles, [(TPA)RhIII(kappa2-(C,N)-CH2CH2(NR)2-]Cl; TPA=N,N,N,N-tris(2-pyridylmethyl)amine have been accessed through treatment of the RhI ethylene complex, [(TPA)Rh(eta2-CH2CH2)]Cl ([1]Cl) with substituted diazenes. We show this methodology to be tolerant of electron-deficient azo compounds including azo diesters (RCO2N?NCO2R; R=Et [3]Cl, R=iPr [4]Cl, R=tBu [5]Cl, and R=Bn [6]Cl) and a cyclic azo diamide: 4-phenyl-1,2,4-triazole-3,5-dione (PTAD), [7]Cl. The latter complex features two ortho-fused ring systems and constitutes the first 3-rhoda-1,2-diazabicyclo[3.3.0]octane. Preliminary evidence suggests that these complexes result from N-N coordination followed by insertion of ethylene into a [Rh]-N bond. In terms of reactivity, [3]Cl and [4]Cl successfully undergo ring-opening using p-toluenesulfonic acid, affording the Rh chlorides, [(TPA)RhIII(Cl)(kappa1-(C)-CH2CH2(NCO2R)(NHCO2R)]OTs; [13]OTs and [14]OTs. Deprotection of [5]Cl using trifluoroacetic acid was also found to give an ethyl substituted, end-on coordinated diazene [(TPA)RhIII(kappa2-(C,N)-CH2CH2(NH)2-]+ [16]Cl, a hitherto unreported motif. Treatment of [16]Cl with acetyl chloride resulted in the bisacetylated adduct [(TPA)RhIII(kappa2-(C,N)-CH2CH2(NAc)2-]+, [17]Cl. Treatment of [1]Cl with AcN?NAc did not give the Rh-N insertion product, but instead the N,O-chelated complex [(TPA)RhI(kappa2-(O,N)-CH3(CO)(NH)(N?C(CH3)(OCH?CH2))]Cl [23]Cl, presumably through insertion of ethylene into a [Rh]-O bond.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI