Search results for "ligand"
showing 10 items of 2559 documents
Equilibrium and structural studies of complexes with a hexadentate ligand containing amide, amine and pyridyl nitrogen donors. Crystal structures of …
2002
A novel potentially hexadentate ligand, 1,8-bis(2-pyridylcarbamoyl)-3,6-diazaoctane (pyctrien) has been synthesised as its tetrahydrochloride salt; its protonation constants and the stability constants of the copper(II) and nickel(II) chelates have been determined by potentiometry. Amide group deprotonation permits the formation of [MLH−1]+ and [MLH−2] species in all cases, whereas the detection of the neutral or the protonated species depends on the nature of the metal ions. The solid complexes of copper, nickel and cobalt with the neutral and the deprotonated ligand have been synthesised and characterised by IR and UV–VIS spectroscopy. The amidic groups are coordinated through the oxygen …
Structural Origin of Metal Specificity in Isatin Hydrolase from Labrenzia aggregata Investigated by Computer Simulations.
2017
We performed quantum-chemical calculations, ab initio molecular dynamics, hybrid quantum mechanics/molecular mechanics (QM/MM) and enhanced sampling metadynamics simulations to investigate the origin of metal specificity in isatin hydrolase from Labrenzia aggregata. The peculiar octahedral binding geometry of the Mn2+ ion in the Michaelis complex includes both the isatin substrate and the catalytic water within the first coordination shell of the cation. Our calculations show that the same arrangement of the ligands cannot be efficiently achieved in the presence of other small divalent metal cations such as Zn2+ or Cu2+ . On the contrary, bulkier alkaline-earth cations such as Mg2+ , which …
Asymmetric [N–I–N]+halonium complexes in solution?
2020
Assessment of the solution equilibria of [bis(pyridine)iodine(I)]+ complexes by ESI-MS and NMR reveals the preference of iodine(I) to form complexes with a more basic pyridine. Mixtures of symmetric [bis(pyridine)iodine(I)]+ complexes undergo statistical ligand exchange, with a predominant entropic driving force favoring asymmetric systems. The influence of ligand basicity, concentration, temperature, and ligand composition is evaluated. Our findings are expected to facilitate the investigations, and the supramolecular and synthetic applications of halonium ions’ halogen bonds. peerReviewed
On the Complexation of Cu(II) and Cd(II) With Polycarboxyl Ligands. Potentiometric Studies With ISE-H+, ISE-Cu2+, and ISE-Cd2+
2009
The interaction of Cu2+ and Cd2+ ions with polyacrylates (PAA, 2 kDa and 100 kDa), polymetacrylate(PMA, 5.4 kDa), and alginate (AA, 70 kDa to 100 kDa) was studied by potentiometry, using ISE-Cu2+, ISE-Cd2+, and ISE-H+ electrodes. The investigations were performed in NaNO3 aqueous solutions, in the ionic strength range 0.10 e I (mol ·L-1) e 0.75, at T ) 298.15 K. The “diprotic-like model” was used to explain the acid-base behavior of the polycarboxylates under investigation (for this model, the monomeric unit of the polyelectrolyte is considered as a dicarboxylate). The results give evidence for the formation of the ML species in all the systems investigated. In addition, the MLH species was…
Impact of Organoaluminum Compounds on Phenoxyimine Ligands in Coordinative Olefin Polymerization. A Theoretical Study
2013
The reduction of the phenoxyimine moiety in three individual species—namely free ligand, aluminum complex, and titanium complex—with aluminum alkyls and aluminum hydride has been studied by means of DFT. It was demonstrated that the free phenoxyimine ligand in an equimolar mixture with trimethylaluminum does not undergo reduction. Instead, experimentally observed formation of the six-membered cyclic aluminum–phenoxyimine complex, useful in the ring-opening polymerization of lactones, takes place as the kinetically and thermodynamically favored process. However, it is anticipated that a 2-fold excess of the aluminum compound, especially aluminum hydride, acting on the resulting cyclic comple…
An Off-On-Off Fluorescent Sensor for pH Windows Based on the 13aneN4-Zn 2+ System
2016
International audience; The new ligand L was prepared and features a 13-membered tetraaza macrocyclic ring with a 1,8-naphthalimide fluorophore appended to a C atom of its backbone. The protonation constants of L as well as its complexation constants with Zn2+ ions were determined in 1:1 water/methanol solutions by potentiometric titrations. Fluorimetric pH titrations were performed with L alone and L in the presence of Zn2+ ions (1:1), and the species distributions (%) versus pH were compared. A window-shaped fluorescence trend was observed with pH for the L/Zn2+ system, which behaves as an off-on-off pH sensor. The on window is centred in the 6.5-7.5 pH range, in correspondence with the f…
The fnr Gene of Bacillus licheniformis and the Cysteine Ligands of the C-Terminal FeS Cluster
1998
Many of the O2-responsive gene regulators of bacteria are members of the fumarate nitrate reductase-cyclic AMP receptor protein family of transcriptional regulators (12, 13, 15, 17) with predicted structures similar to those of the cyclic AMP receptor protein (11). The Fnr (stands for fumarate nitrate reductase regulator) protein from Escherichia coli (FnrEc) controls the expression of a variety of genes, mainly of anaerobic respiration and metabolism (5, 13). It contains a N-terminal cluster of three essential cysteine residues which are supposed to bind together with Cys122 a [4Fe 4S]2+ cluster which is required for O2 sensing (4, 7, 8, 10, 16). A wide variety of gram-negative bacteria co…
Synthesis, Characterization, and Cu(2+) Coordination Studies of a 3-Hydroxy-4-pyridinone Aza Scorpiand Derivative.
2016
The synthesis, acid-base behavior, and Cu(2+) coordination chemistry of a new ligand (L1) consisting of an azamacrocyclic core appended with a lateral chain containing a 3-hydroxy-2-methyl-4(1H)-pyridinone group have been studied by potentiometry, cyclic voltammetry, and NMR and UV-vis spectroscopy. UV-vis and NMR studies showed that phenolate group was protonated at the highest pH values [log K = 9.72(1)]. Potentiometric studies point out the formation of Cu(2+) complexes of 1:2, 2:2, 4:3, 1:1, and 2:1 Cu(2+)/L1 stoichiometries. UV-vis analysis and electrochemical studies evidence the implication of the pyridinone moieties in the metal coordination of the 1:2 Cu(2+)/L1 complexes. L1 shows …
Tailoring polymers through interplay of ligands within precatalysts: 8-(Nitro/benzhydryl-arylimino)-7,7-dimethyl-5,6-dihydroquinolylnickel halides in…
2017
A series of 8-(nitro/benzhydryl-substituted arylimino)-7,7-dimethyl-5,6-dihydroquinolines and the corresponding nickel halide complexes were synthesized and characterized. Molecular structures of representative nickel complexes were determined by single crystal X-ray diffraction, showing the dinuclear dimers with distorted square-pyramidal geometry around the nickel center. The binding energies determined by X-ray photoelectron spectroscopy (XPS) indicate the effective coordination between the sp2-nitrogen and nickel atoms as well as the influence of both the halogen ligands and the substituents within dihydroquinolines on the strength of the NiN bond. Ethylene polymerization with the nicke…
Bis[S-hexyl 3-(thiophen-2-ylmethylidene)dithiocarbazato-κ2N3,S]palladium(II)
2016
In the title complex, [Pd(C12H17N2S3)2], the PdIIatom exhibits a square-planar coordination geometry with theN,S-chelating ligands arranged in atransconfiguration. Intramolecular C—H...S hydrogen bonds are observed. In the crystal, molecules are linked by weak C—H...N hydrogen-bond interactions, forming chains parallel to thebaxis.