Facile solution routes to hydrocarbon-soluble Lewis base adducts of thorium tetrahalides. Synthesis, characterization, and x-ray structure of ThBr4(THF)4

Clark, David L.; Frankcom, Tracey M.; Miller, Matthew J.; Watkin, John G.

doi:10.1021/ic00035a021

Cited by 45 publications

(54 citation statements)

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“…The soluble actinide-halide complexes are regularly explored due to them being possible starting materials for other compounds [39] lead Kiplinger et al to begin developing methods that did not require thorium metal as a starting material. [40] This was done in prior reports [39b] through the reaction of ThCl 4 (DME) 2 , where DME = 1,2-dimethoxyethane, and trimethylsilyl iodide via complete halide exchange to give ThI 4 (DME) 2 .…”

Section: 18mentioning

confidence: 99%

Thorium coordination: A comprehensive review based on coordination number

Tutson

Gorden

2017

Coordination Chemistry Reviews

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Although thorium comprises roughly 8.1 ppm of the Earth, its chemical characteristics and properties have been relatively underexplored. In large part due to its radioactivity and propensity to form oxides at pH above 5, thorium has been much less extensively investigated than first row transition metals. Today, there are close to 700,000 registered structures with an R-factor of 0.075 or better on the Cambridge Crystallographic Database, about 50% of which are complexes containing transition metals. The actinides make up roughly 8% of total number of database structures, with close to 85% of those being uranium containing complexes and 11% of the actinide structures containing thorium. Herein, we explore the various unique coordination environments of thorium with coordination numbers ranging from 5 to 12.

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Section: 18mentioning

confidence: 99%

Thorium coordination: A comprehensive review based on coordination number

Tutson

Gorden

2017

Coordination Chemistry Reviews

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“…Our search for a thorium tetraiodide precursor began with the classic synthon ThI 4 (THF) 4 (1). As shown in eqn (1), reaction of thorium metal turnings (10 g) with 2 equivalents I 2 in THF at 0 °C gave a white powder in ∼80% yield as described in the literature synthesis of 1.…”

Section: And Thi 3 [O(ch 2 ) 4 I](thf)mentioning

confidence: 99%

“…One of the key breakthroughs in inorganic and organometallic thorium chemistry was the development of a convenient synthesis of the Lewis base adducts, ThX 4 (THF) 4 (X = Br, I; THF = tetrahydrofuran), by Clark and co-workers in 1992. 1 The ThX 4 (THF) 4 complexes were prepared under mild conditions by dissolving thorium turnings with elemental bromine or iodine in THF. This solution route represented a significant advance over previous methods to thorium tetrahalides, ThX 4 (X = Cl, Br, I), which required special equipment, hazardous reagents, and high temperatures.…”

Section: Introductionmentioning

confidence: 99%

“…This solution route represented a significant advance over previous methods to thorium tetrahalides, ThX 4 (X = Cl, Br, I), which required special equipment, hazardous reagents, and high temperatures. 1,2 However, over the past two decades, thorium metal has become increasingly difficult to obtain; this has hindered progress in thorium research. To ensure the future vitality of thorium chemistry, routes that do not rely upon thorium metal must be developed for the synthesis of thorium halide or pseudohalide starting materials.…”

Section: Introductionmentioning

confidence: 99%

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Thorium-mediated ring-opening of tetrahydrofuran and the development of a new thorium starting material: preparation and chemistry of ThI4(DME)2

et al. 2012

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The thorium(IV) tetraiodide complex ThI(4)(DME)(2) (3) (DME = 1,2-dimethoxyethane) has been prepared in high yield by reacting the corresponding chloride complex ThCl(4)(DME)(2) with an excess of trimethylsilyl iodide (Me(3)SiI) in toluene. This new route avoids the use of thorium metal as a reagent. ThI(4)(DME)(2) (3) exhibits excellent thermal stability compared to ThI(4)(THF)(4) (1), which undergoes rapid ring-opening of THF at ambient temperature to yield the iodobutoxide complex ThI(3)[O(CH(2))(4)I](THF)(3) (2). Subsequent ligand-exchange between 2 and DME affords ThI(3)[O(CH(2))(4)I](DME)(2) (11), which can be converted to 3 with Me(3)SiI. Salt metathesis between 2 and K(L(Me)) (L(Me) = (2,6-(i)Pr(2)C(6)H(3))NC(Me)CHC(Me)N(2,6-(i)Pr(2)C(6)H(3))) cleanly gives (L(Me))ThI(2)[O(CH(2))(4)I](THF) (10), which is a rare example of a thorium β-diketiminate complex. Complexes 2, 10, and 11 represent the first reported examples of THF ring-opening mediated by thorium. The synthetic utility of ThI(4)(DME)(2) (3) is demonstrated by preparation of thorium(IV) alkoxide, amide, and organometallic compounds.

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“…An example is the isolation of a molecular Th(III) complex [107040-62-0], Th[η- (25). Reports (26) on the synthesis of soluble Th(II) complexes, such as ThI 2 (NCCH 3 ) 2 [85613- , have become suspect (27).…”

Section: Coordination Complexesmentioning

confidence: 99%

Thorium and Thorium Compounds

Clark¹,

Keogh²,

Neu³

et al. 2000

Kirk-Othmer Encyclopedia of Chemical Technology

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Thorium, a naturally occurring radioisotope, and thorium compounds, primarily where thorium is present in the +4 oxidation state, are discussed. The main interest in thorium is as a nuclear fuel, but thorium and its compounds have many specialty uses, for instance, as gas, lantern mantels, and catalysts. Thorium has a rich coordination and organometallic chemistry. 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. Health and safety factors essential for working with thorium are discussed.

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Facile solution routes to hydrocarbon-soluble Lewis base adducts of thorium tetrahalides. Synthesis, characterization, and x-ray structure of ThBr4(THF)4

Cited by 45 publications

References 0 publications

Thorium coordination: A comprehensive review based on coordination number

Thorium coordination: A comprehensive review based on coordination number

Thorium-mediated ring-opening of tetrahydrofuran and the development of a new thorium starting material: preparation and chemistry of ThI4(DME)2

Thorium and Thorium Compounds

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