Coordination Chemistry of Gold Catalysts in Solution: A Detailed NMR Study

Coordination chemistry of gold catalysts bearing eight different ligands [L=PPh₃, JohnPhos (L2), Xphos (L3), DTBP, IMes, IPr, dppf, S‐tolBINAP (L8)] has been studied by NMR spectroscopy in solution at room temperature. Cationic or neutral mononuclear complexes LAuX (L=L2, L3, IMes, IPr; X=charged or neutral ligand) underwent simple ligand exchange without giving any higher coordinate complexes. For L2AuX the following ligand strength series was determined: MeOH?hex‐3‐yne <MeCN≈OTf^??Me₂S<2,6‐lutidine<4‐picoline<CF₃CO₂^?≈DMAP<TMTU<PPh₃<OH^?≈Cl^?. Some heteroligand complexes DTBPAuX exist in solution in equilibrium with the corresponding symmetrical species. Binuclear complexes dppf(AuOTf)₂ and S‐tolBINAP(AuOTf)₂ showed different behavior in exchange reactions with ligands depending on the ligand strength. Thus, PPh₃ causes abstraction of one gold atom to give mononuclear complexes LLAuPPh₃⁺ and (Ph₃P)_nAu⁺, but other N and S ligands give ordinary dicationic species LL(AuNu)₂²⁺. In reactions with different bases, LAu⁺ provided new oxonium ions whose chemistry was also studied: (DTBPAu)₃O⁺, (L2Au)₂OH⁺, (L2Au)₃O⁺, (L3Au)₂OH⁺, and (IMesAu)₂OH⁺. Ultimately, formation of gold hydroxide LAuOH (L=L2, L3, IMes) was studied. Ligand‐ or base‐assisted interconversions between (L2Au)₂OH⁺, (L2Au)₃O⁺, and L2AuOH are described. Reactions of dppf(AuOTf)₂ and S‐tolBINAP(AuOTf)₂ with bases provided more interesting oxonium ions, whose molecular composition was found to be [dppf(Au)₂]₃O₂²⁺, L8(Au)₂OH⁺, and [L8(Au)₂]₃O₂²⁺, but their exact structure was not established. Several reactions between different oxonium species were conducted to observe mixed heteroligand oxonium species. Reaction of L2AuNCMe⁺ with S^2? was studied; several new complexes with sulfide are described. For many reversible reactions the corresponding equilibrium constants were determined.     

Reverse fragment based drug discovery approach via simple estimation of fragment contributions

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Influence of pyridine-based ligands on photostability of MAPbI3 thin films

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A Bis-Chelating / Ligand for the Synthesis of Heterobimetallic Platinum(II)/Rhenium(I) Complexes: Tools for the Optimization of a New Class of Platinum(II) Anticancer Agents

The two independent and coordination sites of a newly synthesized bis[2-(hydroxyphenyl)-1,2,4-triazole] platform have been exploited to prepare four monometallic neutral ()Pt^II complexes carrying DMSO, pyridine, triphenylphosphine, or N-heterocyclic carbene as the fourth ligand. Then, the second coordination site was used to introduce an IR-active rhenium tricarbonyl entity, affording the four corresponding heterobimetallic neutral Pt^II/Re^I complexes, as well as a cationic Pt^II/Re^I derivative. X-ray crystallographic studies showed that distortion of the organic platform occurred to accommodate the coordination geometry of both metal centers. No ligand exchange or transchelation occurred upon incubation of the Pt^II complexes in aqueous environment or in the presence of Fe^III, respectively. The antiproliferative activity of the ligand and complexes was first screened on the triple-negative breast cancer cell line MDA-MB-231. Then, the IC₅₀ values of the most active candidates were determined on a wider panel of human cancer cells (MDA-MB-231, MCF-7, and A2780), as well as on a nontumorigenic cell line (MCF-10A). Low micromolar activities were reached for the complexes carrying a DMSO ligand, making them the first examples of highly active, but hydrolytically stable, Pt^II complexes. Finally, the characteristic mid-IR signature of the {Re(CO)₃} fragment in the Pt/Re heterobimetallic complexes was used to quantify their uptake in breast cancer cells.     

Synthesis and Characterization of Some Novel Dialkyldithiophosphate Derivatives of Macrocyclic Complexes of Pb(II) Having N2 S2 Potential Donors in 14- to 20-Membered Rings

Dialkyldithiophosphate derivatives of macrocyclic complexes of Pb(II), having N₂S₂ potential donors, of the general formula, [Pb(L)S₂P(OR)₂] (where L = macrocyclic ligands L¹, L², L³, L⁴ & L⁵ and R = CH₃-, C₃H₇ ⁿ- & C₃H₇ ⁱ-) have been Synthesized from the reactions of [Pb(L)X₂] (where X = Cl, NO₃, or CH₃COO) with sodium dialkyl dithiophosphates in 1:2 molar ratios in THF. Fifteen new derivatives have been synthesized by the combination of five macrocyclic complexes of 14–20 member rings with three different types of dialkyldithiophosphate. These compounds have been characterized by elemental analysis, molar conductance, molecular weight determination, IR, ¹H NMR, ¹³C, and ³¹P NMR. Molecular weight determinations of these complexes indicate their monomeric nature. An octahedral structure is proposed.     

Dinuclear Nickel(II) and Zinc(II) Complexes of 2,6-[N,N′-bis(2-hydroxyphenylmethyl)-N,N′-bis(2-pyridylmethyl)aminomethyl]-4-methylphenol

Abstract

The symmetric 'end-off' compartmental proligand 2,6-[N,N′-bis(2-hydroxy-phenylmethyl)-N,N′-bis(2-pyridylmethyl)aminomethyl]-4-methylphenol (H₃L) has been used to generate homodinuclear nickel(II) and zinc(II) complexes. The crystal structures of the complexes reveal that the di-nickel(II) complex is donor asymmetric and the di-zinc(II) complex is coordination number asymmetric. In both complexes non-coordinated acetic acid molecules are tightly hydrogen-bonded to the pendant phenols of the ligand generating a double acid salt of the type[CH₃COO…H…L…H…OOCCH₃]^3? in the dinickel complex and a single acid salt of the type [CH₃COO…H…L]^3? in the dizinc complex. In both cases the ligand periphery has been extended to provide a supraligand in which the donor potential of the original ligand has been enhanced.     

Three coordination polymers of 5-aminoisophthalic acid with similar benzimidazole derivative ligands: synthesis,structure and DNA-binding studies

Three novel coordination polymers, [Co(NH₂-Aip)(H₂Bibim)] _n (1), [Co(NH₂-Aip)(HBibimop)] _n  √ nH₂O (2) and [Mn(NH₂-Aip) √ H₂O] _n  √ 2nH₂O (3) with NH₂-Aip and similar benzimidazole derivative ligands (NH₂-Aip = 5-aminoisophthalic acid, H₂Bibim = 2,2′-bibenzimidazole and HBibimop = 1,3-bis(benzimidazol-2-yl)-2-oxapropane), have been synthesised under hydrothermal conditions and structurally characterised by single-crystal X-ray diffraction analysis, elemental analysis and IR spectroscopy. 5-Aminoisophthalic acid ligand adopts μ₂-, μ₃- and μ₄-bridge coordination fashion and benzimidazole derivatives exist as terminal- and bridge-mode in complexes 1–3. The intricate hydrogen bonds and π–π stacking interactions in supramolecular framework are discussed. Using the combination of ultraviolet–visible absorption titration and fluorescence spectra, the experimental results show that complexes 1 and 2 bind to DNA in an intercalative mode and their DNA-binding constants (K _b ) are also found.     

Stability of AgIII towards Halides in Organosilver(III) Complexes

The involvement of silver in two-electron Ag^I/Ag^III processes is currently emerging. However, the range of stability of the required and uncommon Ag^III species is virtually unknown. Here, the stability of Ag^III towards the whole set of halide ligands in the organosilver(III) complex frame [(CF₃)₃AgX]⁻ (X=F, Cl, Br, I, At) is theoretically analyzed. The results obtained depend on a single factor: the nature of X. Even the softest and least electronegative halides (I and At) are found to form reasonably stable Ag^III−X bonds. Our estimates were confirmed by experiment. The whole series of nonradiative halide complexes [PPh₄][(CF₃)₃AgX] (X=F, Cl, Br, I) has been experimentally prepared and all its constituents have been isolated in pure form. The pseudohalides [PPh₄][(CF₃)₃AgCN] and [PPh₄][(CF₃)₃Ag(N₃)] have also been isolated, the latter being the first silver(III) azido complex. Except for the iodo compound, all the crystal and molecular structures have been established by single-crystal X-ray diffraction methods. The decomposition paths of the [(CF₃)₃AgX]⁻ entities at the unimolecular level have been examined in the gas phase by multistage mass spectrometry (MSⁿ). The experimental detection of the two series of mixed complexes [CF₃AgX]⁻ and [FAgX]⁻ arising from the corresponding parent species [(CF₃)₃AgX]⁻ demonstrate that the Ag−X bond is particularly robust. Our experimental observations are rationalized with the aid of theoretical methods. Smooth variation with the electronegativity of X is also observed in the thermolyses of bulk samples. The thermal stability in the solid state gradually decreases from X=F (145 °C, dec.) to X=I (78 °C, dec.) The experimentally established compatibility of Ag^III with the heaviest halides is of particular relevance to silver-mediated or silver-catalyzed processes.     

A novel nanoscale fin field effect transistor by amended channel: Investigation and fundamental physics

The present paper proposes a new Fin Field Effect Transistor (FinFET) with an amended Channel (AC). The fin region consists of two sections; the lower part which has a rounded shape and the upper part of fin as conventional FinFETs, is cubic. The AC-FinFET devices are proven to have a lower threshold voltage roll-off, reduced DIBL, better subthreshold slope characteristics, and a better gate capacitance in comparison with the C-FinFET. Moreover, the simulation result with three-dimensional and two-carrier device simulator demonstrates an improved output characteristic of the proposed structure due to reduction of self-heating effect. Due to the rounded shape of the lower fin region and decreasing corner effects there, the heat can flow easily, and the device temperature will decrease. Also the gate control over the channel increases due to the narrow upper part of the fin. The paper, thus, attempts to show the advantages of higher performance AC-FinFET device over the conventional one, and its effect on the operation of nanoscale devices.