Tetranuclear oxido-bridged thorium(<scp>iv</scp>) clusters obtained using tridentate Schiff bases

Tsantis, Sokratis T.; Lagou-Rekka, Aimilia; Konidaris, Konstantis F.; Raptopoulou, Catherine P.; Bekiari, Vlasoula; Psycharis, Vassilis; Perlepes, Spyros P.

doi:10.1039/c9dt03189h

Cited by 10 publications

(11 citation statements)

References 83 publications

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“…This review can be considered as a continuation of the interest of our group in some aspects of An chemistry [13][14][15][16] and coordination chemistry of Schiff bases with 3d [17,18], 4f [19][20][21] and 5f-metal [15,16] ions, with emphasis on dinuclear and polynuclear complexes and their magnetic, optical and catalytic properties.…”

Section: Scope and Organization Of This Reviewmentioning

confidence: 99%

“…The highest known nuclearity in Th(IV)-Schiff base chemistry is four and the oligonuclear complexes come from our laboratories [16]. The reactions between Th(NO 3 ) 4 •5H 2 O and N-salicylideneo-aminophenol (H 2 L 5 in Figure 13) and N-salicylidene-o-amino-4-methylphenol (H 2 L 6 in Figure 13) in MeCN (without or with the addition of an external base) led to yellowish orange complexes [Th 4 O(NO 3 ) 2 (HL 5 ) 2 (L 5 ) 5 ] (7) and [Th 4 O(NO 3 ) 2 (HL 6 ) 2 (L 6 ) 5 ] (8), respectively, with ≈40% yields (Equation 5).…”

Section: Two Tetranuclear Thorium(iv) Complexesmentioning

confidence: 99%

“…of Et3N, in the presence of excess Ag(NO3) in DMF, yielding {(CH3CH2)3NH}2[(UO2)2(NO3)2(sal)2] (16a), where the geometry around uranyl(VI) center is hexagonal bipyramidal; sal is the salicylate(2-) ligand. Two-phase (H2O/CHCl3) extraction studies of uranyl(VI) ions from aqueous solutions at different pH conditions employing H3L 16 indicates better efficiency at higher pH (99%, pH 5). Compound H3L 16 was selected for the extraction studies due to its better solubility in CHCl3.…”

Section: Dinuclear Uranyl(vi) Complexesmentioning

confidence: 99%

“…Two-phase (H2O/CHCl3) extraction studies of uranyl(VI) ions from aqueous solutions at different pH conditions employing H3L 16 indicates better efficiency at higher pH (99%, pH 5). Compound H3L 16 was selected for the extraction studies due to its better solubility in CHCl3.…”

Section: Dinuclear Uranyl(vi) Complexesmentioning

confidence: 99%

“…Reactions between solution of [(Me2AlOU V O)(H2 Me L 1 )(py)2] (this compound represents the first example of reductive functionalization of the uranyl oxido group by Al III ) with either 1 or 2 equiv. of the strong base MeLi gives solely [Li2(U V O2)2(H2 Me L 1 )2(py)2] (51) in moderate yield (≈40%); Equation (16). Each Li I ion is coordinated to two imine nitrogen atoms; it is also bound to the uranyl endo-oxido atom and a py molecule.…”

Section: Dinuclear and Oligonuclear Uranyl(v) Complexesmentioning

confidence: 99%

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Oligonuclear Actinoid Complexes with Schiff Bases as Ligands—Older Achievements and Recent Progress

Tsantis

Tzimopoulos

Hołyńska

et al. 2020

IJMS

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Even 155 years after their first synthesis, Schiff bases continue to surprise inorganic chemists. Schiff-base ligands have played a major role in the development of modern coordination chemistry because of their relevance to a number of interdisciplinary research fields. The chemistry, properties and applications of transition metal and lanthanoid complexes with Schiff-base ligands are now quite mature. On the contrary, the coordination chemistry of Schiff bases with actinoid (5f-metal) ions is an emerging area, and impressive research discoveries have appeared in the last 10 years or so. The chemistry of actinoid ions continues to attract the intense interest of many inorganic groups around the world. Important scientific challenges are the understanding the basic chemistry associated with handling and recycling of nuclear materials; investigating the redox properties of these elements and the formation of complexes with unusual metal oxidation states; discovering materials for the recovery of trans-{UVIO2}2+ from the oceans; elucidating and manipulating actinoid-element multiple bonds; discovering methods to carry out multi-electron reactions; and improving the 5f-metal ions’ potential for activation of small molecules. The study of 5f-metal complexes with Schiff-base ligands is a currently “hot” topic for a variety of reasons, including issues of synthetic inorganic chemistry, metalosupramolecular chemistry, homogeneous catalysis, separation strategies for nuclear fuel processing and nuclear waste management, bioinorganic and environmental chemistry, materials chemistry and theoretical chemistry. This almost-comprehensive review, covers aspects of synthetic chemistry, reactivity and the properties of dinuclear and oligonuclear actinoid complexes based on Schiff-base ligands. Our work focuses on the significant advances that have occurred since 2000, with special attention on recent developments. The review is divided into eight sections (chapters). After an introductory section describing the organization of the scientific information, Sections 2 and 3 deal with general information about Schiff bases and their coordination chemistry, and the chemistry of actinoids, respectively. Section 4 highlights the relevance of Schiff bases to actinoid chemistry. Sections 5–7 are the “main menu” of the scientific meal of this review. The discussion is arranged according the actinoid (only for Np, Th and U are Schiff-base complexes known). Sections 5 and 7 are further arranged into parts according to the oxidation states of Np and U, respectively, because the coordination chemistry of these metals is very much dependent on their oxidation state. In Section 8, some concluding comments are presented and a brief prognosis for the future is attempted.

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Section: Scope and Organization Of This Reviewmentioning

confidence: 99%

Section: Two Tetranuclear Thorium(iv) Complexesmentioning

confidence: 99%

Section: Dinuclear Uranyl(vi) Complexesmentioning

confidence: 99%

Section: Dinuclear Uranyl(vi) Complexesmentioning

confidence: 99%

Section: Dinuclear and Oligonuclear Uranyl(v) Complexesmentioning

confidence: 99%

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Oligonuclear Actinoid Complexes with Schiff Bases as Ligands—Older Achievements and Recent Progress

Tsantis

Tzimopoulos

Hołyńska

et al. 2020

IJMS

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The Reactivity of Multidentate Schiff Base Ligands Derived from Bi‐ and Terphenyl Polyamines towards M(II) (M=Ni, Cu, Zn, Cd) and M(III) (M=Co, Y, Lu)

et al. 2021

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Multidentate Schiff base ligands derived from a selection of biphenyl-and terphenyl polyamines were synthesized, and their reactivity towards divalent (Ni, Cu, Zn, Cd) and trivalent (Co, Y, Lu) metals was studied by single-crystal X-ray diffraction analysis, NMR spectroscopy, and UV/Vis spectroscopy for the Cu(II) complexes. Large variations in the resulting complexes were observed based on the relative position of the amine substituents in the parent triamines, as well as the electronic properties of the Schiff base ligand itself. Most notably, Schiff base ligands derived from a m-terphenyl-2,2',2''-triamine were found to coordinate in a tetradentate, pentadentate or hexadentate fashion, depending on the size and the valency of the corresponding metal center.

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Inverse Coordination Complexes: Oxygen as Coordination Center

Haiduc¹

2021

Comprehensive Coordination Chemistry III

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Tetranuclear oxido-bridged thorium(iv) clusters obtained using tridentate Schiff bases

Abstract: The reactions of tetravalent thorium, an element named after the Scandinavian God of thunder and war, with tridentate Schiff bases give tetranuclear complexes with the extremely rare {ThIV4(μ4-O)} unit and interesting properties.

Cited by 10 publications

References 83 publications

Oligonuclear Actinoid Complexes with Schiff Bases as Ligands—Older Achievements and Recent Progress

Oligonuclear Actinoid Complexes with Schiff Bases as Ligands—Older Achievements and Recent Progress

The Reactivity of Multidentate Schiff Base Ligands Derived from Bi‐ and Terphenyl Polyamines towards M(II) (M=Ni, Cu, Zn, Cd) and M(III) (M=Co, Y, Lu)

Inverse Coordination Complexes: Oxygen as Coordination Center

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