Home About us Contact
|
Home About us Contact | ||
|
|
||
Ln3+ Ions (ln3+ + ion)
Selected AbstractsStability Constants and Dissociation Rates of the EDTMP Complexes of Samarium(III) and Yttrium(III)EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 30 2008Ferenc Krisztián Kálmán Abstract The stability constants of Sm(EDTMP) (log,KML = 20.71) and Y(EDTMP) (log,KML = 19.19) were determined by a competition reaction between the Ln3+ ion (Ln3+ = Sm3+ or Y3+) and Cu2+ for the EDTMP ligand by spectrophotometry at pH , 10, in the presence of an excess amount of citrate (0.15 M NaCl, 25 °C). For determining the stability constants of Cu(EDTMP) (log,KML = 19.36) and Ca(EDTMP) (log,KML = 8.71) pH,potentiometry was used. In the pH range 4,9 the EDTMP complexes are present in the form of nonprotonated and mono-, di- and triprotonated species. The Ca2+ ion forms a dinuclear complex with Ln(EDTMP). In a simplified blood plasma model consisting of Sm3+, Ca2+ and Zn2+ metal ions, EDTMP, citrate, cysteine and histidine ligands, Sm3+ is practically present in the form of [Sm(HEDTMP)Ca]2,, whereas Zn2+ predominantly forms [Zn(HEDTMP)]5, and [Zn(H2EDTMP)]4, complexes. For studying the dissociation rates of the complexes, the kinetics of the metal exchange (transmetallation) reactions between the Ln(EDTMP) complexes and Cu2+,citrate were investigated in the pH range 7,9 by the stopped-flow method. The rates of the exchange reactions are independent of the Cu2+ concentration and increase with the H+ concentration. The rate constants, characterizing the proton-assisted dissociation of the Ln(EDTMP) complexes, are several orders of magnitude higher than those of the similar Ln(EDTA) complexes, because the protonation constants of Ln(EDTMP) are high and the protonated Ln(HEDTMP) and Ln(H2EDTMP) species are present in higher concentration. The half-times of dissociation of Sm(EDTMP) and Y(EDTMP) at pH = 7.4 and 25 °C are 4.9 and 7.5 s, respectively. These relatively short dissociation half-time values do not predict the deposition of Ln3+ ions in bones in the form of intact Ln(EDTMP) complexes. It is more probable that sorption of the EDTMP ligand and Sm3+ or Y3+ ions occurs independently after the dissociation of complexes.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Anomalous concentration dependence of the coordination behavior of Cl, ion to Ln3+ ion (Ln3+ = rare-earth ion) in anhydrous LnCl3 alcohol solutionsJOURNAL OF RAMAN SPECTROSCOPY, Issue 7 2007Y. Yoshimura Abstract Raman spectroscopic measurements were carried out for the anhydrous LnCl3·20ROH·XLiCl solutions (Ln3+ = La3+, Lu3+, X = 0,3; ROH = MeOH, EtOH, n -PrOH) in the liquid state. The salt concentration (X) dependence of the wavenumber for the Ln,Cl stretching Raman band (,Ln,Cl) is examined in conjunction with the formation of chloro-rare-earth complexes. We have obtained very intriguing results including the fact that the chloro complexations of the middle rare-earth ions (e.g. gadolinium, holmium ions, etc.) in the MeOH and EtOH solutions show peculiar behavior with regard to the salt concentration dependence: the ,Ln,Cl wavenumber increases with the increasing chloride concentration. However, the ,Ln,Cl wavenumbers of the light and heavy rare-earth (e.g. lanthanum, lutetium, etc.) salt solutions show normal behavior; i.e. ,Ln,Cl decreases with the increasing chloride concentration. On the other hand, in the n -PrOH solutions, the ,Ln,Cl frequency in the solutions of all the rare-earth elements exhibits a normal behavior. We now present a possible mechanism for this anomalous concentration dependence of coordination of Cl, ions to Ln3+ ions in anhydrous LnCl3 alcohol solutions. Copyright © 2007 John Wiley & Sons, Ltd. [source] Stability Constants and Dissociation Rates of the EDTMP Complexes of Samarium(III) and Yttrium(III)EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 30 2008Ferenc Krisztián Kálmán Abstract The stability constants of Sm(EDTMP) (log,KML = 20.71) and Y(EDTMP) (log,KML = 19.19) were determined by a competition reaction between the Ln3+ ion (Ln3+ = Sm3+ or Y3+) and Cu2+ for the EDTMP ligand by spectrophotometry at pH , 10, in the presence of an excess amount of citrate (0.15 M NaCl, 25 °C). For determining the stability constants of Cu(EDTMP) (log,KML = 19.36) and Ca(EDTMP) (log,KML = 8.71) pH,potentiometry was used. In the pH range 4,9 the EDTMP complexes are present in the form of nonprotonated and mono-, di- and triprotonated species. The Ca2+ ion forms a dinuclear complex with Ln(EDTMP). In a simplified blood plasma model consisting of Sm3+, Ca2+ and Zn2+ metal ions, EDTMP, citrate, cysteine and histidine ligands, Sm3+ is practically present in the form of [Sm(HEDTMP)Ca]2,, whereas Zn2+ predominantly forms [Zn(HEDTMP)]5, and [Zn(H2EDTMP)]4, complexes. For studying the dissociation rates of the complexes, the kinetics of the metal exchange (transmetallation) reactions between the Ln(EDTMP) complexes and Cu2+,citrate were investigated in the pH range 7,9 by the stopped-flow method. The rates of the exchange reactions are independent of the Cu2+ concentration and increase with the H+ concentration. The rate constants, characterizing the proton-assisted dissociation of the Ln(EDTMP) complexes, are several orders of magnitude higher than those of the similar Ln(EDTA) complexes, because the protonation constants of Ln(EDTMP) are high and the protonated Ln(HEDTMP) and Ln(H2EDTMP) species are present in higher concentration. The half-times of dissociation of Sm(EDTMP) and Y(EDTMP) at pH = 7.4 and 25 °C are 4.9 and 7.5 s, respectively. These relatively short dissociation half-time values do not predict the deposition of Ln3+ ions in bones in the form of intact Ln(EDTMP) complexes. It is more probable that sorption of the EDTMP ligand and Sm3+ or Y3+ ions occurs independently after the dissociation of complexes.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Nitrogen-Rich Compounds of the Lanthanoids: The 5,5,-Azobis[1H -tetrazol-1-ides] of some Yttric Earths (Tb, Dy, Ho, Er, Tm, Yb, and Lu)HELVETICA CHIMICA ACTA, Issue 7 2009Georg Steinhauser Abstract A set of N-rich salts, 3,9, of the heavy lanthanoids (terbium, 3; dysprosium, 4; holmium 5; erbium, 6; thulium, 7; ytterbium, 8; lutetium, 9) based on the energetic 5,5,-azobis[1H -tetrazole] (H2ZT) was synthesized and characterized by elemental analysis, vibrational (IR and Raman) spectroscopy, and X-ray structure determination. The synthesis of the lanthanoid salts 3,9 was performed by crystallization from concentrated aqueous solutions of disodium 5,5,-azobis[1H -tetrazol-1-ide] dihydrate (Na2ZT,2,H2O; 1) and the respective Ln(NO3)3,5,H2O and yielded large rhombic crystals of the type [Ln(H2O)8]2(ZT)3,6,H2O in ca. 70% of the theoretical yield. The compounds 3,9 are isostructural (triclinic space group P) to the previously published yttrium salt 2; they show, however, a clear lanthanoid contraction of several crystallographic parameters, e.g., the cell volume or the LnO bond lengths of the Ln3+ ions and the coordinating H2O molecules. The lanthanoid contraction influences the strengths of the H-bonds, which can be observed as a red shift by 4,cm,1 in the characteristic IR band, in particular from 3595,cm,1 (3) to 3599,cm,1 (9). In good agreement with previous works, 2,9 are purely salt-like compounds without a coordinative bond between the tetrazolide anion and the Ln3+ cation. [source] Modulation of the Lifetime of Water Bound to Lanthanide Metal Ions in Complexes with Ligands Derived from 1,4,7,10-Tetraazacyclododecane Tetraacetate (DOTA)HELVETICA CHIMICA ACTA, Issue 5 2005Shanrong Zhang A series of di- and tetraamide derivatives of DOTA were synthesized, and their lanthanide(III) complexes were examined by multinuclear 1H-, 13C-, and 17O-NMR spectroscopy, and compared with literature data of similar, known complexes (Table). All ligands formed structures similar to the parent [LnIII(DOTA)], complexes, with four N-atoms and four O-atoms from DOTA and one O-atom from the inner-sphere water molecules. Interestingly, the lifetimes ,M of the inner-sphere, metal-bound water molecules vary widely, ranging from nano- to milliseconds, depending on the identity of the pendent amide side chains. In general, positively charged [LnIII(DOTA-tetraamide)]3+ complexes display the longest residence times (high ,M values), while complexes with additional charged functional groups on the extended amides display much smaller ,M values, even when the side groups are not directly coordinated to the central Ln3+ ions. The design of novel [LnIII(DOTA-tetraamide)]3+ complexes with a wide, tunable range of ,M values is of prime importance for the application of fast-responding, paramagnetic chemical-exchange-saturation-transfer (PARACEST) imaging agents used for the study of physiological and metabolic processes. [source] Anomalous concentration dependence of the coordination behavior of Cl, ion to Ln3+ ion (Ln3+ = rare-earth ion) in anhydrous LnCl3 alcohol solutionsJOURNAL OF RAMAN SPECTROSCOPY, Issue 7 2007Y. Yoshimura Abstract Raman spectroscopic measurements were carried out for the anhydrous LnCl3·20ROH·XLiCl solutions (Ln3+ = La3+, Lu3+, X = 0,3; ROH = MeOH, EtOH, n -PrOH) in the liquid state. The salt concentration (X) dependence of the wavenumber for the Ln,Cl stretching Raman band (,Ln,Cl) is examined in conjunction with the formation of chloro-rare-earth complexes. We have obtained very intriguing results including the fact that the chloro complexations of the middle rare-earth ions (e.g. gadolinium, holmium ions, etc.) in the MeOH and EtOH solutions show peculiar behavior with regard to the salt concentration dependence: the ,Ln,Cl wavenumber increases with the increasing chloride concentration. However, the ,Ln,Cl wavenumbers of the light and heavy rare-earth (e.g. lanthanum, lutetium, etc.) salt solutions show normal behavior; i.e. ,Ln,Cl decreases with the increasing chloride concentration. On the other hand, in the n -PrOH solutions, the ,Ln,Cl frequency in the solutions of all the rare-earth elements exhibits a normal behavior. We now present a possible mechanism for this anomalous concentration dependence of coordination of Cl, ions to Ln3+ ions in anhydrous LnCl3 alcohol solutions. Copyright © 2007 John Wiley & Sons, Ltd. [source] Synthesis and Reactivity of Rare Earth Metal Alkyl Complexes Stabilized by Anilido Phosphinimine and Amino Phosphine LigandsCHEMISTRY - A EUROPEAN JOURNAL, Issue 3 2007Bo Liu Abstract Anilido phosphinimino ancillary ligand H2L1 reacted with one equivalent of rare earth metal trialkyl [Ln{CH2Si(CH3)3}3(thf)2] (Ln=Y, Lu) to afford rare earth metal monoalkyl complexes [L1LnCH2Si(CH3)3(THF)] (1,a: Ln=Y; 1,b: Ln=Lu). In this process, deprotonation of H2L1 by one metal alkyl species was followed by intramolecular CH activation of the phenyl group of the phosphine moiety to generate dianionic species L1 with release of two equivalnts of tetramethylsilane. Ligand L1 coordinates to Ln3+ ions in a rare C,N,N tridentate mode. Complex l,a reacted readily with two equivalents of 2,6-diisopropylaniline to give the corresponding bis-amido complex [(HL1)LnY(NHC6H3iPr2 -2,6)2] (2) selectively, that is, the CH activation of the phenyl group is reversible. When 1,a was exposed to moisture, the hydrolyzed dimeric complex [{(HL1)Y(OH)}2](OH)2 (3) was isolated. Treatment of [Ln{CH2Si(CH3)3}3(thf)2] with amino phosphine ligands HL2-R gave stable rare earth metal bis-alkyl complexes [(L2-R)Ln{CH2Si(CH3)3}2(thf)] (4,a: Ln=Y, R=Me; 4,b: Ln=Lu, R=Me; 4,c: Ln=Y, R=iPr; 4,d: Ln=Y, R=iPr) in high yields. No proton abstraction from the ligand was observed. Amination of 4,a and 4,c with 2,6-diisopropylaniline afforded the bis-amido counterparts [(L2-R)Y(NHC6H3iPr2 -2,6)2(thf)] (5,a: R=Me; 5,b: R=iPr). Complexes 1,a,b and 4,a,d initiated the ring-opening polymerization of d,l -lactide with high activity to give atactic polylactides. [source] | ||||||||||