Search results for "Protonation"

Asymmetric bis-(μ1,1-azido) bridged dinuclear copper(II) complex with N2O donor Schiff base: synthesis, structure and magnetic study

2015

A copper(II) complex, [Cu2(L)2(N3)2] [where HL = 2-((3-(methylamino)propylimino)methyl)-6-methoxyphenol] has been synthesized and characterized by elemental analysis, IR, UV–vis and fluorescence spectroscopy, and single-crystal X-ray diffraction studies. The complex crystallizes in the trigonal space group R. The deprotonated tridentate Schiff base occupies three coordination sites of copper(II). The fourth coordination site is occupied by an azide. A symmetry-related azide from a different molecule coordinates with the fifth site of copper(II), thereby forming a double end-on azide-bridged centrosymmetric dimer. Variable temperature solid–state magnetic studies between 2 and 300 K were car…

Copper(II) complexes with 1,5-bis(2-hydroxybenzaldehyde)carbohydrazone

2014

Abstract The acid–base properties of 1,5-bis(2-hydroxybenzaldehyde)carbohydrazone (H4L) and its thioanalogue 1,5-bis(2-hydroxybenzaldehyde)thiocarbohydrazone (H4LS) have been studied experimentally by pH-potentiometry and UV–Vis spectrophotometry and theoretically by using DFT methods. Copper(II) complexes [Cu2(HL)(DMSO)2(H2O)]NO3·H2O (1), [{Cu2(HL)(DMF)(H2O)}n][{Cu2(HL)(DMF)NO3}n](NO3)n (2), [Cu2(HL)(DMF)2(H2O)]HSO4·H2O (3), [Cu2(HL)(DMF)2(H2O)][Cu2(HL)(SO4)(H2O)(DMF)2]·2H2O (4) and [Cu4(HL)2(HSO4)(DMF)2]HSO4 (5), where H4L = 1,5-bis(2-hydroxybenzaldehyde)carbohydrazone, have been synthesised. Complexes 1–3 have been characterised by elemental analysis, IR spectroscopy, ESI mass spectromet…

A Simple Method for the Consecutive Determination of Protonation Constants through Evaluation of Formation Curves

2013

A simple method is presented for the consecutive determination of protonation constants of polyprotic acids based on their formation curves. The procedure is based on generally known equations that describe dissociation equilibria. It has been demonstrated through simulation that the values obtained through the proposed method are sufficiently consistent with the actual values. In contrast with the universally known and applied Bjerrum’s method, no differences in the accuracy of determination of subsequent protonation constant values are observed. The proposed method requires the value of one of the protonation constants (e.g., of the first one, K1) of the polyprotic acid. An iterative meth…

Sequestration of (CH3)Hg+ by amino‐polycarboxylic chelating agents

2012

Abstract The speciation of mono-methylmercury(II) cation (MeHg+) in the presence of Nitrilotriacetate (NTA), Ethylenediamine-N,N,N′,N′-tetraacetate (EDTA), diethylenetriamine-N,N,N′,N″,N″-pentaacetate (DTPA) and (S,S)- Ethylenediamine-N,N′-disuccinic acid (S,S-EDDS) was investigated at I = 0.1 mol L− 1 (NaCl) with the aim to assess a trend of sequestering capacity of the amino‐polycarboxylic (APCs) ligand class towards this cation in aqueous solution. The results obtained gave evidence for the formation of a mononuclear [MeHg(APC)] complex species, differently protonated MeHg(HiL) species (i = 1 to 3, depending on the APC considered), a mixed hydroxo species [MeHg(APC)(OH)] and a binuclear …

Acid-base properties of halloysite clay nanotubes in NaCl medium

2014

Modelling of protonation constants of halloysite clay nanotubes in various aqueous media, at different ionic strengths

2015

In the last decade nanoparticles have assumed more and more importance because of their particular properties mainly due to the nanometer-scale dimensions that confer them a large surface/volume ratio. Among nanomaterials one of the most studied is the halloysite that, as well as the other natural clay minerals is safe for human and environmental friendly. Halloysite is abundant and cheap and is present in large deposits worldwide like those in New Zealand, France, Belgium and China [1,2]. It is similar to kaolin but has a hollow tubular structure that can be attributable to particular crystallization conditions. Typically, halloysite nanotubes (HNTs) are formed by 15 – 20 aluminosilicate l…

Bimodal Acidity at the Amorphous Silica/Water Interface

2015

International audience; Understanding the microscopic origin of the acid base behavior of mineral surfaces in contact with water is still a challenging task, for both the experimental and the theoretical communities. Even for a relatively simple material, such as silica, the origin of the bimodal acidity behavior is still a debated topic. In this contribution we calculate the acidity of single sites on the humid silica surface represented by a model for the hydroxylated amorphous surface. Using a thermodynamic integration approach based on ab initio molecular dynamics, we identify two different acidity values. In particular, some convex geminals and some type of vicinals are very acidic (pK…

Reactivity of antitumor coinage metal-based N-heterocyclic carbene complexes with cysteine and selenocysteine protein sites

2021

Abstract The reaction of the antitumor M(I)-bis-N-heterocyclic carbene (M(I)-NHC) complexes, M = Cu, Ag, and Au, with their potential protein binding sites, i.e. cysteine and selenocysteine, was investigated by means of density functional theory approaches. Capped cysteine and selenocysteine were employed to better model the corresponding residues environment within peptide structures. By assuming the neutral or deprotonated form of the side chains of these amino acids and by considering the possible assistance of an external proton donor such as an adjacent acidic residue or the acidic component of the surrounding buffer environment, we devised five possible routes leading to the binding o…

Modeling the acid-base properties of molybdate(VI) in different ionic media, ionic strengths and temperatures, by EDH, SIT and Pitzer equations

2017

This paper reports the results of a study on the determination of the protonation constants of MoO42 −, in NaClaq, NaNO3aq, KClaq, at different ionic strengths (0 < I/mol dm− 3 ≤ 5.0 in NaClaq, 0 < I/mol dm− 3 ≤ 3.0 in NaNO3aq and KClaq) and temperatures (278.15 ≤ T/K ≤ 318.15 in NaClaq, only 298.15 K in NaNO3aq and KClaq), by potentiometric (ISE-H+ glass electrode) and spectrophotometric (UV/Vis) titrations. After a critical analysis of results and literature findings, the proposed speciation model takes into account the formation of two monomeric and four heptameric species, namely: MoO4H−, MoO4H2, (MoO4)7H86 −, (MoO4)7H95 −, (MoO4)7H104 − and (MoO4)7H113 −. Due to the complexity of…

Synthesis of chiral oxazolidin-2-ones from N-alkoxycarbonyl amino epoxides: a computational studyElectronic supplementary information (ESI) available…

2002

threo-N-Alkoxycarbonylamino epoxides 5a–d, containing the oxazolidine moiety, were converted into trans-4,5-disubstituted-2-oxazolidin-2-ones 2 with total regio- and stereoselection by means of nucleophilic intramolecular attack of the carbamate moiety to the protonated oxirane ring. Theoretical calculations confirmed both the regioselection and the preference of the cyclocarbamation reaction vs. the intermolecular attack by the solvent, arising from different behaviour in comparison with the analogous iodonium ions.