The crystal structure of tetranitratobis(triphenylphosphine oxide)thorium(IV)

Malik, K. M. Abdul; Jeffery, J. W.

doi:10.1107/s0567740873007375

Cited by 13 publications

(6 citation statements)

References 6 publications

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“…While cyclometalated aryloxide ligands have been observed in a number of crystallographically characterized transition metal complexes, especially of group 5, we believe 7 to be the first example of a structurally characterized cyclometalated aryloxide ligand in f-element chemistry. The Th−O distance to the triphenylphosphine oxide ligand is 2.445(7) Å, which is comparable to the distances of 2.376(10) (av), 2.35(2) (av), and 2.36(1) Å found for the triphenylphosphine oxide ligands in ThCl 4 (OPPh 3 ) 3 , Th(NO 3 ) 4 (OPPh 3 ) 2 , and Th(NO 3 ) 2 (C 17 H 13 N 2 O 2 ) 2 (OPPh 3 ) 2 3 ORTEP representation (40% probability ellipsoids) of the molecular structure of Cp*Th(OC 6 H 3 - t -BuCMe 2 CH 2 )(OAr)(OPPh 3 ) ( 7 ) giving the atom-numbering scheme used in the tables. 4 Selected Bond Distances (Å) and Angles (deg) for Cp*Th(OC 6 H 3 - t -BuCMe 2 CH 2 )(OAr)(OPPh 3 ) ( 7 ) Th(1)−C(25)2.521(12)Th(1)−O(1)2.445(7) Th(1)−O(2)2.205(7)Th(1)−O(3)2.192(6) Th(1)−Cp*(cent)2.62(1)Th(1)−Cp*(av)2.88(4) Cp*(cent)−Th(1)−O(3)168.3(3)Cp*(cent)−Th(1)−C(25)99.2(3) Cp*(cent)−Th(1)−O(2)101.4(3)Cp*(cent)−Th(1)−O(1)98.7(3) O(3)−Th(1)−C(25)70.6(3)O(3)−Th(1)−O(2)86.9(3) O(3)−Th(1)−O(1)80.5(2)O(1)−Th(1)−C(25)111.6(3) O(2)−Th(1)−C(25)104.4(3)O(1)−Th(1)−O(2)134.9(3) Th(1)−C(25)−C(26)116.8(8)Th(1)−O(1)−P(1)166.6(4) Th(1)−O(2)−C(19)162.6(6)Th(1)−O(3)−C(32)148.4(6)

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Section: Resultssupporting

confidence: 59%

Mono(pentamethylcyclopentadienyl)thorium Chemistry: Synthesis, Structural Characterization, and Reactivity of Aryloxide and Alkyl Derivatives

et al. 1996

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Reaction of ThBr4(THF)4 with 1 equiv of Cp*MgBr(THF) (Cp* = η-C5Me5) produces the mono(pentamethylcyclopentadienyl) complex Cp*ThBr3(THF)3 (1). Treatment of 1 with 1 or 2 equiv of KOAr (Ar = 2,6-t-Bu2C6H3) yields the mono- and bis(aryloxide) species Cp*ThBr2(OAr)(THF) (2) and Cp*ThBr(OAr)2 (3), respectively. Alkylation of 2 with 2 equiv of Me3SiCH2MgCl leads to isolation of the bis(alkyl) complex Cp*Th(OAr)(CH2SiMe3)2 (4), while 3 reacts with 1 equiv of MeMgBr to form the mono(alkyl) derivative Cp*ThMe(OAr)2 (5). 4 reacts with dihydrogen to produce the trimeric thorium dihydride [Cp*ThH2(OAr)]3 (6), while thermolysis of 4 in the presence of triphenylphosphine oxide leads to the isolation of the metallacyclic species Cp*Th(OC6H3-t-BuCMe2CH2)(OAr)(OPPh3) (7). In the presence of 1 equiv of [HNMe2Ph][B(C6F5)4], 4 is found to catalyze the hydrogenation of 1-hexene and also the polymerization of ethylene. Compounds 1−7 have been characterized by 1H NMR and IR spectroscopy, by microanalysis, and, in the case of 3, 4, and 7, by single-crystal X-ray diffraction studies. Cp*ThBr(OAr)2 (3) exhibits a somewhat distorted three-legged piano-stool geometry with Th−Cp*centroid, Th−O, and Th−Br distances of 2.57(1), 2.16(1) (av), and 2.821(2) Å, respectively. Cp*Th(OAr)(CH2SiMe3)2 (4) also displays a three-legged piano-stool geometry with Th−C distances to the alkyl groups of 2.460(9) and 2.488(12) Å. Th−Cp*centroid and Th−O distances are very similar to those found in 3, at 2.53(1) and 2.186(6) Å, respectively. Cp*Th(OC6H3-t-BuCMe2CH2)(OAr)(OPPh3) (7) features a distorted trigonal bipyramidal geometry about the metal center, with the Cp* ligand and the oxygen atom of the cyclometalated aryloxide ligand occupying axial sites (Cp*centroid−Th−O = 168.3(3)°). The Th−C distance to the tert-butyl methylene group is 2.521(12) Å, while Th−O distances to the aryloxide and triphenylphosphine oxide ligands are 2.199(7) (av) and 2.445(7) Å, respectively.

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…”

Section: Resultssupporting

confidence: 59%

Mono(pentamethylcyclopentadienyl)thorium Chemistry: Synthesis, Structural Characterization, and Reactivity of Aryloxide and Alkyl Derivatives

et al. 1996

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“…For this work, the calixarene has been recalculated with the MM3 and CONFLEX procedures, and the same conformation was found, albeit with a much lower energy, 230 kJ mol −1 . The molecule of each complex was built taking into account the experimental data reported above and in the literature. ,,,, The structures refined by performing optimized geometry calculations as well as their associated thermodynamic parameters are collected in Table . The main bond lengths and bond angles of the coordination polyhedra of the thorium complexes are collected in Table S1 (Supporting Information).…”

Section: Resultsmentioning

confidence: 99%

“…Radiotoxicity of the actinides is a limitation in the development of their coordination chemistry. Therefore, analogue cations are often studied, for example, Eu(III) for Pu(III), Am(III), and Cm(III); Th(IV) for U(IV) and Pu(IV); and UO 2 2+ for NpO 2 2+ and PuO 2 2+ . , The most explored complexes are those of uranium and thorium. ,– ,– Coordination numbers (CN) ranging from 6 to 12 have been found for thorium(IV) complexes with neutral and charged organic ligands, ,,,, CN = 8 and 9 with square antiprismatic and trigonal prismatic geometries being the most common. Th(IV) complexes with macrocycles such as porphyrins and calixarenes are also known.…”

Section: Introductionmentioning

confidence: 99%

Physicochemical Properties and Theoretical Modeling of Actinide Complexes with a para-tert-Butylcalix[6]arene Bearing Phosphinoyl Pendants. Extraction Capability of the Calixarene toward f Elements

et al. 2008

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The coordination ability of the hexaphosphinoylated p-tert-butylcalix[6]arene B6bL6 toward actinides is established, as well as its good separation ability of the actinide ions UO2 2+ and Th(IV) over trivalent rare earths such as La(III), Eu(III), and Y(III). Spectrophotometric titration of uranyl with B6bL6 in CH 3CN yields log beta 11 = 7.1 and log beta 12 = 12.5 for the 1:1 and 1:2 (UO2 2+/B 6bL6) species, respectively. Actinide complexes with 1:1 and 1:2 (M/L) stoichiometries are isolated and characterized by elemental analysis, IR, and UV-vis. Compounds 1 and 3 fulfill their CN = 8 just with B 6bL (6), while compounds 2 and 4 require coordinated nitrates and/or water molecules. The luminescence spectra of the uranyl complexes and the parameters such as FWMH, vibronic spacing (upsilon sp), and the U-O bond length, as well as the luminescence lifetimes, permit the understanding of the coordination chemistry of these actinide calixarene complexes. Energy transfer from the B6bL6 ligand to the uranyl ion is demonstrated to be relevant in compound 1 with Q abs = 2.0%. The uranyl complex emission reveals a biexponential decay with tau s from 210 to 220 micros and tau L from 490 to 650 micros for compounds 1 and 3, respectively. The liquid-liquid extraction results demonstrate the good extraction capability of B 6bL (6) toward actinides but not for rare earths at room temperature. The extracted species keeps the 1(cation)/1(calixarene) ratio for the UO2 2+, Th 4+, and Eu 3+ ions. A good capacity of B6bL 6 toward Th4+ ions using aqueous phase 2 containing even up to 0.3 M thorium nitrate and an organic phase of 2.47 x 10 (-4) M B6bL6 in chloroform is found. The spectroscopic properties of the isolated uranyl complexes and the extraction studies reveal a uranophilic nature of B6bL6. The molecular modeling results are in good agreement with the experimental findings.

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“…Several investigators have reported examples of thorium(IV) coordination numbers of 12, and factors responsible for these unexpectedly high coordination numbers have been briefly discussed. 19,21,23 It has been suggested that the packing in those structures containing nitrate ions is stabilized by short O-O nitrate oxygen atom nonbonded interactions, the thorium(IV) cation size, and the empty 5f electronic configuration. Indeed, the structure of 1 shows two nonbonded oxygen-oxygen atom distances 0(5)-0(6), 2.148 (6) Á, and 0(8)-0(9), 2.147 (7) Á, which are significantly shorter than the sum of oxygen atom ionic radii, 2.8 Á.…”

Section: Resultsmentioning

confidence: 99%

“…The short nitrate ion edge distances represent the "bite" distance in these bidentate ligands, and they are similar to distances reported for MgTh(N03)6-8H2023 and 3. 19 Lastly, the stability of the coordination number of 12 in 1 is further indicated by a comparison of potential coordination choices. In 3, the maximum coordination number available to thorium is 10 since the two phosphoryl ligands each offer only one coordination site.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and crystal and molecular structure of a [diethyl (N,N-diethylcarbamyl)methylenephosphonate]thorium nitrate complex

Bowen¹,

Duesler²,

Paine³

1982

Inorg. Chem.

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261spectively. The boron atom for each of these BF4-groups was placed at coordinates calculated by averaging the corresponding fluorine coordinates. These coordinates were not refined but were recalculated periodically (final boron-boron separation = 0.50 A). The isotropic temperature factors for the boron atoms were refined. The populations for the groups refined to final values of 0.71 and 0.29.The final refinement of the structure was done by block-diagonal least-squares with two matrices. All nonhydrogen positional parameters were included in one matrix; the second contained all nonhydrogen thermal parameters, the BF4-population factor, and the scale factor. No reflections were omitted from this refinement. The final R was 0.051 for the 665 reflections with F:

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The crystal structure of tetranitratobis(triphenylphosphine oxide)thorium(IV)

Cited by 13 publications

References 6 publications

Mono(pentamethylcyclopentadienyl)thorium Chemistry: Synthesis, Structural Characterization, and Reactivity of Aryloxide and Alkyl Derivatives

Mono(pentamethylcyclopentadienyl)thorium Chemistry: Synthesis, Structural Characterization, and Reactivity of Aryloxide and Alkyl Derivatives

Physicochemical Properties and Theoretical Modeling of Actinide Complexes with a para-tert-Butylcalix[6]arene Bearing Phosphinoyl Pendants. Extraction Capability of the Calixarene toward f Elements

Synthesis and crystal and molecular structure of a [diethyl (N,N-diethylcarbamyl)methylenephosphonate]thorium nitrate complex

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