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(Chemical Equation Presented) HOF·CH3CN, a very efficient oxygen-transfer agent, made readily from F2, H2O, and CH3CN, was reacted with various 1,10-phenanthroline derivatives to form the corresponding N,N?-dioxides in good yields and short reaction times.

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Metal catalyst and ligand design,
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A new route to cycloneophylplatinum(II) complexes is reported and the selectivity of protonolysis of the platinum-aryl and -alkyl bonds has been determined. Reaction of [PtCl2(SMe2)2] with neophylmagnesium chloride gives the binuclear cycloneophylplatinum(II) complex [Pt2(CH2CMe2C6H4)2(mu-SMe2)2], 1, which is shown to exist as a mixture of syn and anti isomers. Complex 1 reacts reversibly with SMe2 to give [Pt(CH2CMe2C6H4)(SMe2)2], 2, and irreversibly with bidentate ligands NN = 3,4,7,8-tetramethyl-1,10-phenanthroline (phen?) or 4,4?-di-t-butyl-2,2’bipyridine (bubipy) to give the corresponding complexes [Pt(CH2CMe2C6H4)(phen?)], 3, and [Pt(CH2CMe2C6H4)(bubipy)], 4, respectively. Complex 2 reacts with HCl initially by cleavage of the aryl-platinum bond to give mostly trans-[PtCl(CH2CMe2Ph)(SMe2)2], which then rearranges to an equilibrium mixture with trans-[PtCl(C6H4-2-t-Bu)(SMe2)2], while 3 and 4 react to give [PtCl(CH2CMe2Ph)(phen?)] and [PtCl(CH2CMe2Ph)(bubipy)], which do not undergo the isomerization reaction. The protonolysis reactions occur by way of a platinum(IV) hydride complex in each case, and the unusual reactivity of complex 2 is attributed to the ease of dissociation of the Me2S ligands.

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Metal catalyst and ligand design,
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Borylation of aliphatic C-H bonds in alkylamines and alkyl ethers to form primary aminoalkyl and alkoxyalkyl boronate esters and studies on the origin of the regioselectivity of these reactions are reported. The products of these reactions can be used directly in Suzuki-Miyaura cross-coupling reactions or isolated as air-stable potassium trifluoroborate salts. Selective borylation of the terminal C-H bond at the positions beta to oxygen and nitrogen occurs in preference to borylation of the other terminal C-H bonds. Experimental studies and computational results show that C-H bond cleavage is the rate-determining step of the current borylation reactions. The observed higher reactivity of C-H bonds at the terminal position of ethylamines and ethers results from a combination of attractive Lewis acid-base and hydrogen-bonding interactions, as well as typical repulsive steric interactions, in the transition state. In this transition state, the heteroatom lies directly above the boron atom of one boryl ligand, creating a stabilizing interaction between the weak Lewis acid and Lewis base, and a series of C-H bonds of the substrate lie near the oxygen atoms of the boryl ligands, participating in a set of weak C- H···O interactions that lead to significant stabilization of the transition state forming the major product.

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

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The bis(diphenylphosphino)methane (dppm) compounds of copper(I), (PF6)2 (biL=1,10-phenanthroline and its derivatives), have been synthesized and characterized by (1)H and (31)P NMR spectroscopy and X-ray crystallography.The molecules are found to contain a 2+ framework with the two copper atoms bridged by two dppm ligands to give eight-membered Cu2P4C2 rings.This framework shows a staggered conformation subject to the coordination of additional ligands.The coordination (1)H and (31)P shifts of the dppm are well-correlated with the basicity of the nitrogen donor atom of biL, sensitive to variations in the copper-ligand binding as well as their metal-to-ligand charge-transfer band.Crystallographic data of are as follows, monoclinic space group P21/c, a=11.515(2) Angstroem, b=27.922(4) Angstroem, c=12.493(2) Angstroem, beta=107.68(1), U=3827(1) Angstroem3, and Z=2.

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Metal catalyst and ligand design,
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The combination of nickel metallaphotoredox catalysis, hydrogen atom transfer catalysis, and a Lewis acid activation mode, has led to the development of an arylation method for the selective functionalization of alcohol alpha-hydroxy C?H bonds. This approach employs zinc-mediated alcohol deprotonation to activate alpha-hydroxy C?H bonds while simultaneously suppressing C?O bond formation by inhibiting the formation of nickel alkoxide species. The use of Zn-based Lewis acids also deactivates other hydridic bonds such as alpha-amino and alpha-oxy C?H bonds. This approach facilitates rapid access to benzylic alcohols, an important motif in drug discovery. A 3-step synthesis of the drug Prozac exemplifies the utility of this new method.

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Metal catalyst and ligand design,
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The deuterium isotope effect on the thermodynamic driving force is discussed. Theory correctly predicts a decrease in the kinetic isotope effect as the reaction driving force increases. The observed isotope effect for replacement of H//2O by D//2O is significantly larger than predicted even after correcting for the solvent dependence of the reaction driving force.

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

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The in vitro cytotoxic properties of antimicrobial copper(II) complexes with 3,4,7,8-tetramethyl-1,10-phenanthroline (TMP) or 4,7-dipyridyl-1,10-phenanthroline (DIP) ligands and ruthenium(II) complexes coordinated with TMP or 2,9-dimethyl-1,10-phenanthroline ligands were investigated. Both copper(II) complexes were found to have similar inhibitory concentrations (IC50 ~ 2?2.5 muM). Their cytotoxicity was found to be necrotic, associated with cytoplasmic vacuolisation, rounding, detachment and lack of apoptosis-associated DNA fragmentation, in comparison to the apoptotic effects of cisplatin which demonstrate adherent cell enlargement or detachment, membrane blebbing and condensation. Antimicrobial ruthenium(II) complexes demonstrated a lower renal cytotoxicity than copper(II) complexes or cisplatin (IC50 > 60 muM). [Cu(DIP)(dach)](ClO4)2 and [Cu(TMP)(dach)](ClO4)2 (where dach = 1,2-diaminocyclohexane) induced dihydroethidium-sensitive ROS and the cytotoxicity of both TMP and DIP coordinated copper(II) complexes was mitigated by catalase, highlighting a role of H2O2 generation in their mode of action. The cytotoxicity of either copper(II) complex was not affected by coincubation with organic cation transporter (OCT) inhibitors cimetidine or disopyramide, in contrast to cisplatin, suggesting a non-OCT dependent mode of uptake for the copper(II) complexes in human cells. Coincubation with copper sulfate reduced the cytotoxicity of [Cu(TMP)(dach)](ClO4)2 (3-6 ×). The TMP complex induced a greater degree of G2/M accumulation and micronuclei generation than the DIP complex, possibly attributable to its greater DNA binding affinity. These results highlight the potentially low genotoxicity of copper(II) complexes coordinated with TMP or DIP and polypyridyl ruthenium(II) complexes as potential antimicrobial agents.

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Metal catalyst and ligand design,
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Catalysts function by providing an alternate reaction mechanism that has a lower activation energy than would be found in the absence of the catalyst. In some cases, the catalyzed mechanism may include additional steps.In a article, 1660-93-1, molcular formula is C16H16N2, introducing its new discovery. Quality Control of: 3,4,7,8-Tetramethyl-1,10-phenanthroline

Eight new organometallic Ru(II)-arene complexes of the type [RuCl2(n6-arene)(n1-S-aroylthiourea)] (arene = p-cymene or benzene) were synthesized in order to evaluate the effect of the arene moiety and the substituent of the aroylthiourea ligand on the cytotoxicity of the complexes. The ligands (L1 and L2) and complexes (1-8) were characterized using analytical and spectroscopic (UV-visible, infrared, 1H NMR, 13C NMR, and mass) methods. The structure of the ligands (L1 and L2) and complexes (1 and 3-6) was obtained from single-crystal X-ray diffraction studies. The cytotoxicity of the complexes was evaluated against four different cancer cell lines: MCF-7 (breast), COLO 205 (colon), A549 (lung), and IMR-32 (neuroblastoma). All the complexes showed good cytotoxicity and the highest was in the IMR-32 cell line, which articulates the specificity of these complexes toward the IMR-32 cancer cell line. The complexes 5, 7, and 8 exhibited remarkable cytotoxicity in the entire cancer cell lines tested, which was comparable with the standard drug, cisplatin. The anticancer mechanism of the complexes 3 and 7 in IMR-32 cells was evaluated by bright-field microscopy, intracellular reactive oxygen species (ROS), mitochondrial membrane potential (MMP), DNA damage, and caspase-3 analyses. The cells treated with the complexes showed upregulated caspase-3 compared to the control, and it was found that ROS and MMP were dose-dependent on analysis. Also, bright-field microscopy and 4?,6-diamidino-2-phenylindole (DAPI) staining have correspondingly shown cellular membrane blebbing and DNA damage, which were morphological hallmarks of apoptosis. The study concluded that the complexes promoted the oxidative stress-mediated apoptotic death of the cancer cells through the generation of intracellular ROS, depletion of MMP, and damage of the nuclear material.

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Metal catalyst and ligand design,
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Chemistry is traditionally divided into organic and inorganic chemistry. Product Details of 1660-93-1. The former is the study of compounds containing at least one carbon-hydrogen bonds.In a patent,Which mentioned a new discovery about 1660-93-1

Four new luminescent cyclometallated iridium(iii) bis(quinolylbenzaldehyde) diimine complexes [Ir(qba)2(NN)](PF6) (Hqba = 4-(2-quinolyl)benzaldehyde, NN = 2,2?-bipyridine, bpy (1); 1,10-phenanthroline, phen (2); 3,4,7,8-tetramethyl-1,10-phenanthroline, Me 4-phen (3); 4,7-diphenyl-1,10-phenanthroline, Ph2-phen (4)) have been synthesised and characterised, and their electronic absorption, emission and electrochemical properties investigated. The X-ray crystal structures of complexes 1 and 2 have been determined. Upon irradiation, complexes 1-4 exhibited intense and long-lived orange-yellow emission in fluid solutions at 298 K and in alcohol glass at 77 K. The emission has been assigned to a triplet intra-ligand (3IL) excited state associated with the qba ligand, probably with mixing of some triplet metal-to-ligand charge-transfer (3MLCT) (dpi(Ir) ? pi*(qba)) character. Reductive amination reactions of complexes 1-4 with the protein bovine serum albumin (BSA) afforded the bioconjugates 1-BSA-4-BSA, respectively. Upon photoexcitation, these bioconjugates displayed intense and long-lived 3MLCT (dpi(Ir) ? pi*(NC)) emission in aqueous buffer at 298 K. The cross-linked nature of the Ir-BSA bioconjugates has been verified by SDS-PAGE. Additionally, the cytotoxicity of the complexes towards human cervix epithelioid carcinoma (HeLa) cells has been examined by 3-(4,5-dimethyl-2-thiazolyl)-2,5- diphenyltetrazolium bromide (MTT) assays, and the cellular uptake of complex 4 has been investigated by laser-scanning confocal microscopy and flow cytometry.

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

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A synthesis of the pyridine-linked bisindole alkaloid scalaridine A is described. An iridium catalyzed, directed C-H borylation of N-Boc-5-methoxyindole gave the corresponding 3-borylindole, which underwent a one-pot, double Suzuki-Miyaura cross-coupling reaction with 3,5-dibromopyridine to install the entire heteroaromatic framework of the natural product. Removal of the protecting groups gave a synthetic sample of scalaridine A, which was spectroscopically identical to that described in the isolation report.

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