Thorium (Iv) Metal Complexes With Neutral Oxygen Donor Ligands - A Review

Agarwal, Rakesh; Agarwal, Himanshu; Arora, Kishor

doi:10.1515/revic.2000.20.1.1

Cited by 9 publications

(7 citation statements)

References 4 publications

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“…The predominant ionic character of the bonding leads to a wide variety of coordination numbers (CN) and symmetries. For thorium(IV) complexes, CN = 8 and 9 in square antiprismatic and trigonal prismatic geometries are the most common, although CN ranging from 6 to 12 have been found [1,7,25]. Thorium complexes with calixarenes are known, the most related with this work are complexes with CMPO- [18] and phosphine oxide-derivatized [11,17] calixarenes, whose stoichiometries suggest usually CN = 8-9.…”

Section: Molecular Modelingmentioning

confidence: 69%

“…In fact, electrostatic repulsion and van der Waals interaction energy terms from the ligands are detrimental to the calculated energy of the optimized molecular geometry (Table 1). However, bond lengths and angles are in the usual range for Th-O coordination [7,11]. The Th OP average bond lengths are 2.505 ± 0.025 and 2.521 ± 0.085 Å for 1 and 2, respectively (Supplementary data, Table S1).…”

Section: Th(iv) Complexesmentioning

confidence: 97%

“…It has been reported that extraction of thorium in dichloromethane containing p-tert-butylcalix [4][5][6][7][8]arene diphenylphosphine oxides attached to the lower rim results in the co-extraction of complexes with different stoichiometries; indeed, the slopes of the logD versus log[L] graphs are between 1.8 and 2.6 and coextraction of nitric acid or activity coefficients could not be ruled out [17]. For europium, the slopes are between 2.0 and 2.5.…”

Section: Stoichiometric Correlation Of Extraction-complexation Datamentioning

confidence: 99%

“…Therefore, complexes with weakly a-emitting, long half-life radio-elements such as uranium [2][3][4][5][6] and tetravalent thorium [7] have been the most studied while lanthanide ions (Ln), in an indirect way, have afforded knowledge on the chemical behavior of trivalent actinides [8,9]. Thorium coordination chemistry is also well documented, both with respect to hydration and hydrolysis [10], complexes with oxygen-and nitrogen-donor ligands [7], macrocyclic complexes [11][12][13], and even quadruple-stranded helicates [14].…”

Section: Introductionmentioning

confidence: 99%

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5f-Element complexes with a p-tert-butylcalix[4]arene bearing phosphinoyl pendant arms: Separation from rare earths and structural studies

Ramı́rez

Varbanov

Bünzli

et al. 2011

Inorganica Chimica Acta

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a b s t r a c tPhosphinoylated calixarenes feature high coordination ability toward f elements and a great potentiality toward actinide/rare earth separation. Here, we report three characteristic properties of a tetra-phosphinoylated p-tert-butylcalix[4]arene, B 4 bL 4 functionalized with phosphinoyl pendant arms: (i) its coordination ability toward Th(IV) complexation in organic medium, (ii) its ability to separate thorium from yttrium, lanthanum, and europium in three different organic media, and (iii) the X-ray crystal structure of the La complex. Thorium ( ) n ÁxH 2 O (n = 1, x = 1, 1; n = 2, x = 4, 2). Spectroscopic data point to the inner coordination sphere of 1 and 2 containing nitrate ions and water molecules. Molecular modeling of 1 yielded an 8-coordinate species and its coordination polyhedron can be described as a distorted square antiprism while that for 2, a 9-coordinate species, as a distorted tricapped trigonal prism. The extraction study of tetravalent thorium and trivalent rare-earth (Y, La, Eu) ions from acidic nitrate media by B 4 bL 4 in chloroform shows thorium being much more extracted than the rare earths, with selectivity close to 100%. The extraction behavior can be easily modulated by changing the initial conditions (pH, nitrate concentration

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Section: Molecular Modelingmentioning

confidence: 69%

Section: Th(iv) Complexesmentioning

confidence: 97%

Section: Stoichiometric Correlation Of Extraction-complexation Datamentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

5f-Element complexes with a p-tert-butylcalix[4]arene bearing phosphinoyl pendant arms: Separation from rare earths and structural studies

Ramı́rez

Varbanov

Bünzli

et al. 2011

Inorganica Chimica Acta

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“…The coordination chemistry of thorium(IV) has been less extensively investigated [1][2][3]. Th(IV) with an ionic radius 0.99 Å and a charge of 4+ fulfils the optimum conditions required for a high coordination.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, spectral and thermal investigations of some mixed ligand complexes of thorium(IV) derived from semicarbazones and diphenyl sulfoxide

Agarwal

Prasad

2005

JICS

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In the present work, the authors describe the synthesis of some mixed ligand complexes of thorium(IV) derived from 4[N-(2'-hydroxy-1'-naphthalidene)amino]antipyrine semicarbazone (HNAAPS) or 4[N-(cinnamalidene)amino]antipyrinesemicarbazone (CAAPS) as primary ligand and diphenyl sulfoxide (DPSO) as secondary ligand with the general composition ThX 4 .n(L).DPSO (n = 1, X = Cl, Br, NCS or NO 3 ; n = 2, X = I or ClO 4 , L = HNAAPS or CAAPS). All the compounds were characterized through elemental analysis, molar conductance, molecular weight, infrared data and thermogravimetric analysis. The infrared studies reveal that the semicarbazones behave as neutral tridentate (N,N,O) while DPSO coordinates through its oxygen atom. The nitrates are bicovalently bonded, while thiocyanates are N-coordinated in these compounds. In conclusion, the coordination number of the central metal ion displays coordination number 7, 8, 9 or 12 depending on the nature of the anionic ligands.

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Thorium and Thorium Compounds

Clark

Neu

Runde

et al. 2006

Kirk-Othmer Encyclopedia of Chemical Technology

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An overview is provided on thorium and thorium compounds with an emphasis on their relevance to chemical technology. The main interest in thorium is as a nuclear fuel, but thorium and its compounds have many specialty uses including lantern mantles and catalysts. Discussion on the occurrence, recovery, preparation, properties and radiochemistry of thorium is provided. While not intending to be exhaustive, a broad based review is provided on the coordination and organometallic complexes of thorium with halogens; N, P, and O donors; cyclopentadienyl; annulene; hydrocarbyl; and allyl ligands. A drawback to using thorium in many processes is the chemical reactivity of the metal as well as the inherent radioactivity of all thorium isotopes. As such, health and safety factors essential for working with thorium are discussed. General references from which more detailed information of the aforementioned subjects is provided.

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Thorium (Iv) Metal Complexes With Neutral Oxygen Donor Ligands - A Review

Cited by 9 publications

References 4 publications

5f-Element complexes with a p-tert-butylcalix[4]arene bearing phosphinoyl pendant arms: Separation from rare earths and structural studies

5f-Element complexes with a p-tert-butylcalix[4]arene bearing phosphinoyl pendant arms: Separation from rare earths and structural studies

Synthesis, spectral and thermal investigations of some mixed ligand complexes of thorium(IV) derived from semicarbazones and diphenyl sulfoxide

Thorium and Thorium Compounds

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