Dissociation kinetics study of Ce(III) complexes with H8dotp (H8dotp = 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetrakis (methylphosphonic acid))

Svobodová, Ivona; Piskuła, Zbigniew; Lubal, Přemysl; Lis, Stefan; Hermann, Petr

doi:10.1016/j.jallcom.2007.04.052

Cited by 8 publications

(3 citation statements)

References 18 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Slow diffusion of 1,4‐dioxane to an aged solution of Ce x DOTP y resulted in crystallization of orange‐brown crystals of Ce IV DOTP suitable for X‐ray crystallography analysis. The analogous in‐cage Ce III DOTP was prepared separately according to a known synthetic procedure [41] and was crystallized out of aqueous solutions by slow addition of 1,4‐dioxane. It was also used as an electrochemical precursor for Ce IV DOTP (see below).…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

DOTP versus DOTA as Ligands for Lanthanide Cations: Novel Structurally Characterized Ce^IV and Ce^III Cyclen‐Based Complexes and Clusters in Aqueous Solutions

Dovrat

Pevzner

Maimon

et al. 2022

Chemistry A European J

View full text Add to dashboard Cite

The coordination and redox chemistry of aqueous CeIV/III macrocyclic compounds were studied by using the ligands DOTA and DOTP (1,4,7,10‐tetraazacyclododecane‐1,4,7,10‐tetrayl)tetraacetic acid and 1,4,7,10‐tetraazacyclododecane‐1,4,7,10‐tetra(methylene phosphonic acid), respectively). The hydrolysis tendency of the tetravalent cation in the presence of DOTA is shown to result in the formation of a highly ordered, fluorite‐like [CeIV6(O)4(OH)4(H2O)8(DOTAH)4] oxo‐hydroxo structure both in solution and in the solid state. The lifetime of the analogous species formed in the presence of DOTP was found to be much shorter. Spectroscopic measurements of the latter suggest its similarity to the former. Its gradual decomposition in solution leads to the accumulation of the in‐cage complexes [CeIVDOTP] and [CeIIIDOTP(H2O)], which were crystallographically characterized in this study. The redox energetics and spectroscopic characteristics for the transition between these two in‐cage complexes in aqueous solutions were studied as well. Together with the crystallographic structures of the above‐mentioned species, the in‐cage [CeIVDOTA(H2O)] complex structure is presented herein for the first time. An elaborative analysis of the X‐ray crystallographic structural data obtained for the in‐cage complexes studied herein and similar structures published previously suggests that hard‐bonding cyclen‐derived ligands are, counter‐intuitively, better suited for encapsulating, and perhaps kinetically stabilize softer cations than harder ones with DOTP, marked as a possible adequate chelator for the study of the aqueous properties of LnII and AcIII cations.

show abstract

Section: Resultsmentioning

confidence: 99%

“…Ce III DOTP: The complex was prepared as published before [41] : 19 mg CeCl 3 • 7H 2 O (Sigma-Aldrich) and 28 mg DOTP (Macrocyclics TM ) were weighed and dissolved in 5 mL of deionized H 2 O (10 mM each). 10 > pH > 9 was attained using gentle dropwise addition of 1 M NaOH solution.…”

Section: Complex Synthesismentioning

confidence: 99%

DOTP versus DOTA as Ligands for Lanthanide Cations: Novel Structurally Characterized Ce^IV and Ce^III Cyclen‐Based Complexes and Clusters in Aqueous Solutions

Dovrat

Pevzner

Maimon

et al. 2022

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…5À (300 nm) [60] complexes. Figure 3 shows the example of depenA C H T U N G T R E N N U N G dence of the observed pseudo-first-order rate constant, d k obs , of the Ce III -H 6 L complex on the acidity of solution and temperature.…”

mentioning

confidence: 99%

Lanthanide(III) Complexes of 4,10‐Bis(phosphonomethyl)‐1,4,7,10‐tetraazacyclododecane‐1,7‐diacetic acid (trans‐H₆do2a2p) in Solution and in the Solid State: Structural Studies Along the Series

Campello¹,

Lacerda²,

Pereira

et al. 2010

Chemistry A European J

View full text Add to dashboard Cite

Complexes of 4,10-bis(phosphonomethyl)-1,4,7,10-tetraazacyclododecane-1,7-diacetic acid (trans-H(6)do2a2p, H(6)L) with transition metal and lanthanide(III) ions were investigated. The stability constant values of the divalent and trivalent metal-ion complexes are between the corresponding values of H(4)dota and H(8)dotp complexes, as a consequence of the ligand basicity. The solid-state structures of the ligand and of nine lanthanide(III) complexes were determined by X-ray diffraction. All the complexes are present as twisted-square-antiprismatic isomers and their structures can be divided into two series. The first one involves nona-coordinated complexes of the large lanthanide(III) ions (Ce, Nd, Sm) with a coordinated water molecule. In the series of Sm, Eu, Tb, Dy, Er, Yb, the complexes are octa-coordinated only by the ligand donor atoms and their coordination cages are more irregular. The formation kinetics and the acid-assisted dissociation of several Ln(III)-H(6)L complexes were investigated at different temperatures and compared with analogous data for complexes of other dota-like ligands. The [Ce(L)(H(2)O)](3-) complex is the most kinetically inert among complexes of the investigated lanthanide(III) ions (Ce, Eu, Gd, Yb). Among mixed phosphonate-acetate dota analogues, kinetic inertness of the cerium(III) complexes is increased with a higher number of phosphonate arms in the ligand, whereas the opposite is true for europium(III) complexes. According to the (1)H NMR spectroscopic pseudo-contact shifts for the Ce-Eu and Tb-Yb series, the solution structures of the complexes reflect the structures of the [Ce(HL)(H(2)O)](2-) and [Yb(HL)](2-) anions, respectively, found in the solid state. However, these solution NMR spectroscopic studies showed that there is no unambiguous relation between (31)P/(1)H lanthanide-induced shift (LIS) values and coordination of water in the complexes; the values rather express a relative position of the central ions between the N(4) and O(4) planes.

show abstract

Tris(phosphonomethyl)cyclen Derivatives: Thermodynamic Stability, Kinetics, Solution Structure, and Relaxivity of Ln³⁺ Complexes

et al. 2012

View full text Add to dashboard Cite

International audienceThe lanthanide (Ln3+) complexes of three cyclen-based ligands containing three methylphosphonate pendant arms were studied, the ligands being 1,4,7,10-tetraazacyclododecane-1,4,7-triyltris(methylphosphonic acid) (H6do3p), 3-[4,7,10-tris(phosphonomethyl)-1,4,7,10-tetraazacyclododec-1-yl]propanoic acid (H7do3p1pr), and 10-(3-hydroxypropyl)-1,4,7,10-tetraazacyclododecane-1,4,7-triyltris(methylphosphonic acid) (H6do3p1ol). The three macrocyclic ligands form complexes of very high thermodynamic stability with all studied Ln3+ ions. Kinetic studies showed that the acid-assisted dissociation of Ce3+ complexes of these ligands is much faster than for the complex of the related ligand H8dotp [1,4,7,10-tetraazacyclododecane-1,4,7,10-tetrayltetrakis(methylphosphonic acid)]. The number of water molecules coordinated to the Eu3+ and Gd3+ complexes was estimated to be < 1 for the do3p1ol ligand but ca. 1 for the other two ligands, as obtained by time-resolved luminescence spectroscopy and by 1H and 17O relaxometric measurements. The NMR spectroscopic data indicate the existence of a considerable contribution from second-sphere water molecules to the relaxivity of all the Gd3+ complexes studied. The 1H and 31P NMR spectra of the Eu3+, Yb3+ and Lu3+ complexes showed that the propionate arm in the [Ln(do3p1pr)]4- complexes and the propanol arm in the [Ln(do3p1ol)]3- complexes are not bound to the Ln3+ ion. The [Ln(do3p)]3- and [Ln(do3p1pr)]4- complexes have a clear preference for the TSAP (twisted square antiprismatic) isomer, while both SAP (square antiprismatic) and TSAP isomers are present in solutions of the [Ln(do3p1ol)]3- complexes

show abstract

Dissociation kinetics study of Ce(III) complexes with H8dotp (H8dotp = 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetrakis (methylphosphonic acid))

Cited by 8 publications

References 18 publications

DOTP versus DOTA as Ligands for Lanthanide Cations: Novel Structurally Characterized Ce^IV and Ce^III Cyclen‐Based Complexes and Clusters in Aqueous Solutions

DOTP versus DOTA as Ligands for Lanthanide Cations: Novel Structurally Characterized Ce^IV and Ce^III Cyclen‐Based Complexes and Clusters in Aqueous Solutions

Lanthanide(III) Complexes of 4,10‐Bis(phosphonomethyl)‐1,4,7,10‐tetraazacyclododecane‐1,7‐diacetic acid (trans‐H₆do2a2p) in Solution and in the Solid State: Structural Studies Along the Series

Tris(phosphonomethyl)cyclen Derivatives: Thermodynamic Stability, Kinetics, Solution Structure, and Relaxivity of Ln³⁺ Complexes

Contact Info

Product

Resources

About

Dissociation kinetics study of Ce(III) complexes with H8dotp (H8dotp = 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetrakis (methylphosphonic acid))

Cited by 8 publications

References 18 publications

DOTP versus DOTA as Ligands for Lanthanide Cations: Novel Structurally Characterized CeIV and CeIII Cyclen‐Based Complexes and Clusters in Aqueous Solutions

DOTP versus DOTA as Ligands for Lanthanide Cations: Novel Structurally Characterized CeIV and CeIII Cyclen‐Based Complexes and Clusters in Aqueous Solutions

Lanthanide(III) Complexes of 4,10‐Bis(phosphonomethyl)‐1,4,7,10‐tetraazacyclododecane‐1,7‐diacetic acid (trans‐H6do2a2p) in Solution and in the Solid State: Structural Studies Along the Series

Tris(phosphonomethyl)cyclen Derivatives: Thermodynamic Stability, Kinetics, Solution Structure, and Relaxivity of Ln3+ Complexes

Contact Info

Product

Resources

About

DOTP versus DOTA as Ligands for Lanthanide Cations: Novel Structurally Characterized Ce^IV and Ce^III Cyclen‐Based Complexes and Clusters in Aqueous Solutions

DOTP versus DOTA as Ligands for Lanthanide Cations: Novel Structurally Characterized Ce^IV and Ce^III Cyclen‐Based Complexes and Clusters in Aqueous Solutions

Lanthanide(III) Complexes of 4,10‐Bis(phosphonomethyl)‐1,4,7,10‐tetraazacyclododecane‐1,7‐diacetic acid (trans‐H₆do2a2p) in Solution and in the Solid State: Structural Studies Along the Series

Tris(phosphonomethyl)cyclen Derivatives: Thermodynamic Stability, Kinetics, Solution Structure, and Relaxivity of Ln³⁺ Complexes