scholarly journals Tales of the Unexpected: The Case of Zirconium(IV) Complexes with Desferrioxamine

Molecules ◽  
2019 ◽  
Vol 24 (11) ◽  
pp. 2098 ◽  
Author(s):  
Matteo Savastano ◽  
Carla Bazzicalupi ◽  
Giovanni Ferraro ◽  
Emiliano Fratini ◽  
Paola Gratteri ◽  
...  
Keyword(s):  
Stability Constants ◽  
Density Functional ◽  
Maldi Mass Spectrometry ◽  
Binuclear Complexes ◽  
X Ray Scattering ◽  
Complex Solutions ◽  
The Stability ◽  
Ph Range ◽  
First Time

The Zr4+ complexes with desferrioxamine (H3DFO) and its derivatives are the only 89Zr-based imaging agents for proton emission tomography (PET) that have been used so far in clinical trials. Nevertheless, a complete speciation of the Zr4+/H3DFO system in solution has never been performed and the stability constants of the relevant complexes are still unknown. Here we report, for the first time, the speciation of this system in water, performed by potentiometric titrations, and the determination of the stability constants of all complexes formed in the pH range 2.5–11.5. Surprisingly, although desferrioxamine gives rise to very stable 1:1 complexes with Zr4+ (logK = 36.14 for Zr4+ + DFO3− = [ZrDFO]+), 2:2 and 2:3 ones are also formed in solution. Depending on the conditions, these binuclear complexes can be main species in solution. These results were corroborated by small-angle X-ray scattering (SAXS) and MALDI mass spectrometry analyses of complex solutions. Information on complex structures was obtained by means of density functional theory (DFT) calculations.

The Determination of the Solubility of Amorphous UO2 (Sn and the Mononuclear Hydrolysis Constants of Uranium(IV) at 25° C.

1986 ◽  
Vol 84 ◽  
Author(s):  
Jordi Bruno ◽  
Ignasi Casas ◽  
Bo Lagerman ◽  
Maria Munoz
Keyword(s):  
Stability Constants ◽  
Solubility Data ◽  
Hydrolysis Constants ◽  
Reducing Conditions ◽  
Wide Ph Range ◽  
The Stability ◽  
Ph Range ◽  
Good Agreement

AbstractWe have measured the solubility 8f amorphous UO2in a wide pH range (2 to 10.5), in 0.5 M NaClO, at T=25 C. The species responsible for the solubility are U(OH) + and U'0H)h, with the stability constants lo:1,3=-1.1± 0.1 and log, 4 =- 5.4_.O. 2, respectively. No evidence for U(OH) is f6und up to pH=10.5. The same model explains satisfactorily the solubility data obtained by Parks and Pohl(5) at T=1000 C., in the pH range 1 to 10. The measured solubility of amorphous UO2 (s) in the pH_ýange 6 to 10.5, under reducing conditions, is rather high,. U(IV) =5 10 mols/l. This is in good agreement with previous data of Gayer and Leider(6) and Galkin and Stepanov(9).

Physicochemical investigation on thiomalate complexes of nickel

1968 ◽  
Vol 21 (3) ◽  
pp. 641 ◽  
Author(s):  
RS Saxena ◽  
KC Gupta ◽  
ML Mittal
Keyword(s):  
Aqueous Medium ◽  
Stability Constants ◽  
Alternative Methods ◽  
Acid System ◽  
Kcal Mole ◽  
Physicochemical Investigation ◽  
Different Temperatures ◽  
The Stability ◽  
Ph Range ◽  
Deep Violet

Potentiometric and conductometric studies of the nickel-thiomalic acid system, in aqueous medium of 0. lM KNO3, reveal the formation of two complexes; one light violet 1 : 1 predominating at pH 6.5-7.5 and another deep violet 1 : 2 in the pH range 8.5-10.0. The stability constants of the complexes formed have been determined by applying Calvin and Melchior's extension of Bjerrum's method at three different temperatures and were further refined by using alternative methods. The logK values (final) for 1 : 1 and 1 : 2 complexes at 20, 25, and 30� have been found to be 7.86, 7.87, 7.96, and 6.24, 6.31, 6.39 respectively. The values of the overall changes in ΔG, ΔH, and ΔS accompanying the reaction have also been evaluated at 25� and found to be -19.31 kcal/mole, -8.77 kcal/mole, and +35.36 cal/deg respectively.

Can boron form coordination complexes with diffuse electrons? Evidence for linked solvated electron precursors

2022 ◽  
Author(s):  
Zachary Jordan ◽  
Shahriar N. Khan ◽  
Benjamin A. Jackson ◽  
Evangelos Miliordos
Keyword(s):  
Electronic Structure ◽  
Density Functional ◽  
Molecular System ◽  
Hydrocarbon Chain ◽  
Solvated Electron ◽  
Excitation Energies ◽  
Functional Theory ◽  
Boron Complexes ◽  
The Stability ◽  
First Time

Abstract Density functional theory and ab initio multi-reference calculations are performed to examine the stability and electronic structure of boron complexes that host diffuse electrons in their periphery. Such complexes (solvated electron precursors or SEPs) have been experimentally identified and studied theoretically for several s- and d-block metals. For the first time, we demonstrate that a p-block metalloid element can form a stable SEP when appropriate ligands are chosen. We show that three ammonia and one methyl ligands can displace two of the three boron valence electrons to a peripheral 1s-type orbital. The shell model for these outer electrons is identical to previous SEP systems (1s, 1p, 1d, 2s). Further, we preformed the first examination of a molecular system consisting of two SEPs bridged by a hydrocarbon chain. The electronic structure of these dimers is very similar to that of traditional diatomic molecules forming bonding and anti-bonding σ and π orbitals. Their ground state electronic structure resembles that of two He atoms, and our results indicate that the excitation energies are nearly independent of the chain length for four carbon atoms or longer. These findings pave the way for the development of novel materials similar to expanded metals and electrides.

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