Search results for "Protonation"
showing 10 items of 583 documents
Cu2+and AMP complexation of enlarged tripodal polyamines
2006
The synthesis, characterization, Cu2+ coordination and interaction with AMP of three tripodal polyamines are reported. The polyamines are based on the structure of the tetraamine (tren) which has been enlarged with three propylamino functionalities (TAL), with a further anthrylmethyl fragment at one of its terminal primary nitrogens (ATAL) or with naphthylmethyl fragments at its three ends (N3TAL). The protonation constants of all three polyamines show that at pH 6, all six primary and secondary nitrogen atoms in the arms are protonated. The interaction with Cu2+ and AMP (adenosine-5′-monophosphate) has been studied by potentiometric, UV-Vis, ESI-MS spectroscopy and NMR techniques. pH-Metri…
Diorganotin(IV) N-acetyl-L-cysteinate complexes: synthesis, solid state, solution phase, DFT and biological investigations.
2009
Diorganotin(IV) complexes of N-acetyl-L-cysteine (H(2)NAC; (R)-2-acetamido-3-sulfanylpropanoic acid) have been synthesized and their solid and solution-phase structural configurations investigated by FTIR, Mössbauer, (1)H, (13)C and (119)Sn NMR spectroscopy. FTIR results suggested that in R(2)Sn(IV)NAC (R = Me, Bu, Ph) complexes NAC(2-) behaves as dianionic tridentate ligand coordinating the tin(IV) atom, through ester-type carboxylate, acetate carbonyl oxygen atom and the deprotonated thiolate group. From (119)Sn Mössbauer spectroscopy it could be inferred that the tin atom is pentacoordinated, with equatorial R(2)Sn(IV) trigonal bipyramidal configuration. In DMSO-d(6) solution, NMR spectr…
Colorimetric sensing of anions by a neutral biphenyl based amide receptor
2006
A new colorimetric sensor for fluoride is described. Compound 1 shows an open structure and its behaviour is compared with that of two related closed compounds 2 and 3. In all cases, the red colour developed in the presence of fluoride can be related to deprotonation processes, however ligand 1 gives rise to a faster colour change than 2 or 3 because of its higher flexibility. Other halides as well as carboxylates have been studied and the stoichiometry and complexation constants for the corresponding ligands have been determined.
Biphenyl macrolactams in anion complexation. Selective naked-eye fluoride recognition
2004
Two colorimetric anion sensors 1 and 2 allow for the selective differentiation of fluoride in the presence of other anions. Two different types of species have been observed in the complexation process, one of them is a co-ordination complex and the other is a salt generated by ligand deprotonation. The deprotonation reaction induces a conformational change, giving rise to a symmetrical species. This species is responsible for colour development. Ligand 3 has a similar structure and does not give rise to any colour modification due to presence of the dimethylamino groups in the biphenyl moiety. The X-ray structure of ligand 2 is also reported and compared with that of ligand 1, that had bee…
A polyazacyclophane containing two biphenyl subunits as a versatile cation and anion receptor
2002
Abstract The synthesis, protonation behaviour and coordination capabilities towards Cu 2+ , Zn 2+ and towards the nucleotides ATP and ADP of a cyclophane ditopic receptor 2,6,10,23,27,31-hexaaza[11,11](2,2′)biphenylophane containing two 2,2′-biphenylene spacers linked to the ends of 1,5,9-triazanonane chains are presented.
Polyazapodands Derived from Biphenyl. Study of their Behaviour as Conformationally Regulated Fluorescent Sensors
2004
Eight new polyazapodands containing a 4,4′-substituted biphenyl moiety have been synthesised. Four (7, 8, 9 and 11) are functionalised on positions 4 and 4′ with a nitro group and four (1, 2, 3 and 10) with a dimethylamino substituent. Comparison of the emission behaviour of 1, 2, 3 with that of the reference compounds 10 and tetramthylbenzidine, clearly suggests that a modification in the dihedral angle between the biphenyl rings is an important factor in determining the fluorescent response of the molecule. The fluorescence is pH dependent, due to the formation of intramolecular hydrogen bonds between protonated aliphatic nitrogens and a carbonyl oxygen, which influences the aforementione…
ChemInform Abstract: Experimental and Theoretical Studies on the Electronic Spectra of Indole-3-acetic Acid and Its Anionic and Protonated Species.
2010
Abstract The geometrical and electronic structure of indole-3-acetic acid (IAH) have been investigated using the MINDO/3 molecular orbital method, the geometries being optimized by Rinaldi's method. The UV spectrum of IAH has been recorded in different solvents. The corresponding spectra of IAH + 2 and IA − were also respectively obtained, from IAH in different H 2 SO 4 /water mixtures and NaOH solutions. The agreement of experimental spectra with the ones theoretically calculated by the CNDO/M-Cl method after optimization of the κ parameter, is discussed. The p K a values of IAH have also been determined from the IAH + 2 spectra and are compared with literature data.
Reversible switching of the electronic ground state in a pentacoordinated Cu(ii) complex.
2013
International audience; An easy reversible switching of the electronic ground state in a pentacoordinated copper(ii) complex is reported for the first time. The simple protonation of a carboxylic group in a Cu(ii) complex with a {dx(2)-y(2)}(1) electronic configuration leads to a flip of the ground electronic configuration from {dx(2)-y(2)}(1) to {dz(2)}(1) in the metal ion.
A Rational Design for Imidazolate-Bridged Linear Trinuclear Compounds from Mononuclear Copper(II) Complexes with 2-[((Imidazol-2-ylmethylidene)amino)…
2001
Two mononuclear copper(II) complexes with the unsymmetrical tridentate ligand 2-[((imidazol-2-ylmethylidene)amino)ethyl]pyridine (HL), [Cu(HL)(H2O)](ClO4)2.2H2O (1) and [Cu(HL)Cl2] (2), have been prepared and characterized. The X-ray analysis of 2 revealed that the copper(II) ion assumes a pentacoordinated square pyramidal geometry with an N3Cl2 donor set. When 1 and 2 are treated with an equimolecular amount of potassium hydroxide, the deprotonation of the imidazole moiety promotes a self-assembled process, by coordination of the imidazolate nitrogen atom to a Cu(II) center of an adjacent unit, leading to the polynuclear complexes [[Cu(L)(H2O)](ClO4)]n (3) and [[Cu(L)Cl].2H2O]n (4). Variab…
The Reduction Pathway of End-on Coordinated Dinitrogen. I. Vibrational Spectra of Mo/W−N2, −NNH, and −NNH2 Complexes and Quantum Chemistry Assisted N…
1999
Infrared and Raman spectra of [M(N(2))(2)(dppe)(2)] (M = W, Mo) and the two protonated derivatives [WF(NNH)(dppe)(2)] and [WF(NNH(2))(dppe)(2)](+) (dppe = 1,2-bis(diphenylphosphino)ethane) are presented. Using isotope substituted compounds ((15)N and D) the vibrations of the Y-M-N(2)H(x)() (x = 0, 1, 2; Y = N(2), F) central unit are identified, in particular the M-N and N-N stretching modes. In case of the monoprotonated systems, an equilibrium between metal- and nitrogen-protonated species exists that is clearly detectable in the IR spectra. Making use of theoretical force fields, a quantum chemistry assisted normal coordinate analysis (QCA-NCA) is performed for all three tungsten systems …