Multifunctionality in Two Families of Dinuclear Lanthanide(III) Complexes with a Tridentate Schiff-Base Ligand

Anastasiadis, Nikolaos C.; Granadeiro, Carlos M.; Mayans, Júlia; Raptopoulou, Catherine P.; Bekiari, Vlasoula; Cunha‐Silva, Luís; Psycharis, Vassilis; Escuer, Albert; Balula, Salete S.; Konidaris, Konstantis F.; Perlepes, Spyros P.

doi:10.1021/acs.inorgchem.9b01524

Cited by 13 publications

(14 citation statements)

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“…The six U IV ions have a zig-zag topology [116]. The crystal structure of clusters 59-63 [115,116] underline the remarkable associating capacity of the various anionic forms of the H4L 31 , H4L 32 , H4L 33 and H4L 34 Schiff bases, by achieving a large number of coordination bonds to (19) The use of the potentially hexadentate Schiff base H 4 HO salophen (the structural formula of its dianion has been presented in Figure 3) in uranium(IV) chemistry has provided access to the structurally impressive octanuclear cluster (pyH) 2 [U VI 8 (O) 4 Cl 10 ( HO salophen) 4 ] (57); Equation (20). Each tetra-anionic ligand bridges four U IV centers in a 4.222211 ligation mode [114].…”

Section: Dinuclear and Oligonuclear Uranyl(v) Complexesmentioning

confidence: 97%

“…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%

“…Metal complexes with Schiff bases as ligands continue to attract the intense interest of inorganic chemists due to their relevance to a number of interdisciplinary research fields, including bioinorganic chemistry, molecular magnetism, multifunctional molecular materials, photo-and electroluminescence, energetic materials, sensors, materials with non-linear optical properties, medicinal chemistry, homogeneous and heterogeneous catalysis and multielectron redox chemistry [1,11,[18][19][20][21][22][24][25][26][27][28][29][30], among others. For example, in the field of catalysis, Schiff-base metal complexes can catalyze polymerization, ring-opening polymerization, oxidation, epoxidation, ring opening of epoxides, reduction of ketones, allylic alkylation, hydrosilation of acetophenones, hydrogen peroxide decomposition, Michael addition, annulation, carbonylation, Heck reactions, alanine benzylation, hydrocarbon amidation and aziridination, cyclopropanation, aldehyde silylcyanation, Diels-Alder and aldol condensation reactions, isomerization of norbornadiene to quadricyclone, addition reactions of cyanides to imines and desymmetrization reactions of meso compounds [26,27].…”

Section: Schiff Bases and Their Coordination Chemistrymentioning

confidence: 99%

“…The interesting ligand H5L 19 was synthesized from the 1:2 reaction between 1,3-diamino-2propanol and 3-formylsalicylic acid in refluxing EtOH. Its reaction with 2 equiv.…”

Section: Dinuclear Uranyl(vi) Complexesmentioning

confidence: 99%

“…Selected examples are described below. Clusters (pyH) 3 [ (56) were prepared using the ligands H 4 L 31 and H 4 L 32 (with R = Me), respectively; Equations (18) and (19). Adventitious traces of O 2 were responsible for the U(III) →U(IV) oxidation during the preparation of 56.…”

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: Dinuclear and Oligonuclear Uranyl(v) Complexesmentioning

confidence: 97%

Section: Scope and Organization Of This Reviewmentioning

confidence: 99%

Section: Schiff Bases and Their Coordination Chemistrymentioning

confidence: 99%

“…The interesting ligand H5L 19 was synthesized from the 1:2 reaction between 1,3-diamino-2propanol and 3-formylsalicylic acid in refluxing EtOH. Its reaction with 2 equiv.…”

Section: Dinuclear Uranyl(vi) Complexesmentioning

confidence: 99%

Section: Dinuclear and Oligonuclear Uranyl(v) Complexesmentioning

confidence: 99%

See 3 more Smart Citations

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

Tsantis

Tzimopoulos

Hołyńska

et al. 2020

IJMS

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Effect of Additives in the Hydroamination/Cyclization of Aminoalkenes Catalyzed by a Binaphtholate Yttrium Catalyst

2023

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A series of various solvents and additives were tested in enantioselective hydroamination/cyclization reactions of aminoalkenes catalyzed by a binaphtholate yttrium catalyst. The functional group tolerance of the catalyst and the influence on the reaction rate and enantioselectivity was studied. Some weakly coordinating polar solvents, such as Et2O, MTBE, and chlorobenzene led to slightly increased reaction rates compared to the less polar solvent benzene, presumably due to a better stabilization of the polar transition state. Stronger binding solvents and additives, such as THF, DMAP, pyrrolidine, n‐propylamine, and 1‐phenylethylamine, decrease the reaction rate and diminish the enantioselectivity of the hydroamination product. Some additives, such as THF, Et2O, MTBE, chloro‐ and bromobenzene, as well as (+)‐sparteine resulted in slightly higher enantioselectivities in the cyclization of the model substrate C‐(1‐allylcyclohexyl)methylamine, although this observation was not generally true for other aminoalkene substrates. The reaction rates and enantioselectivities were depressed in the presence of (−)‐sparteine using the (R)‐binaphtholate‐ligated catalyst. In case of C‐(1‐allylcyclohexyl)methylamine, the enantioselectivity was switched from 76% ee favoring the (S)‐enantiomer of the hydroamination product when using (+)‐sparteine to 22% ee in favor of the (R)‐enantiomer when (−)‐sparteine was used. The rates of cyclization of aminoalkenes and the resulting enantioselectivities significantly depend on substrate concentration with the highest rate (13.6 h−1) and enantioselectivity (68% ee) observed in dilute conditions (0.05 M) compared to a concentrated solution (0.5 M, 5.0 h−1, 35% ee) for 2,2‐dimethylpent‐4‐enylamine. These observations indicate that the reaction mechanism is shifted in favor of a slower, less enantioselective catalytic cycle involving a higher coordinate species when higher substrate concentrations or stronger binding additives are present.

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Trapping an Unexpected/Unprecedented Hexanuclear Ce(III) Hydrolysis Product with Neutral 4‐Amino‐1,2,4‐triazole

Wineinger,

Smetana,

Hiti

et al. 2023

Eur J Inorg Chem

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Using Ce(III) as both a representative lanthanide and actinide analog, the ability of mixtures of acidic and basic azoles to allow direct access to homoleptic N‐donor f‐element complexes in one pot reactions from hydrated salts as starting materials was examined by reacting mixtures of 4‐amino‐1,2,4‐triazole (4‐NH2‐1,2,4‐Triaz), 5‐amino‐tetrazole (5‐NH2‐HTetaz), and 1,2,3‐triazole (1,2,3‐HTriaz) in 1:1 and 1:3 ratios with CeCl3•7H2O, [C2mim]3[CeCl6] ([C2mim]+ = 2‐ethyl‐1‐methylimidazolium), and Ce(NO3)3•6H2O. Although unsuccessful in our goal, single crystal X‐ray diffraction revealed that neutral 4‐NH2‐1,2,4‐Triaz is structure directing via h2m2k2 bridging, with the formation of the dinuclear complexes [Ce2Cl2(µ2‐4‐NH2‐1,2,4‐Triaz)4(H2O)8]Cl4•4H2O, [Ce2(µ2‐4‐NH2‐1,2,4‐Triaz)4(4‐NH2‐1,2,4‐Triaz)2(Cl)6], and [4‐NH2‐1,2,4‐HTriaz][Ce2(µ2‐4‐NH2‐1,2,4‐Triaz)2(µ2‐NO3)(NO3)6(H2O)2]. When the synthetic conditions favored hydrolysis, the hexanuclear Ce(III) complex [Ce6(µ3‐O)4(µ3‐OH)2(µ3‐Cl)2(Cl)6(µ2‐4‐NH2‐1,2,4‐Triaz)12]•7H2O was isolated. This unexpected hydrolysis product represents the first example of a high nuclearity lanthanide complex where all Ln atoms are pairwise connected through 12 N‐donor ligands or 12 neutral bridging ligands of any type, a rare example of incorporation of non‐oxo coordinating anions in the M6X8 core, and the first reported Ce(III) hexanuclear complex of this type.

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Multifunctionality in Two Families of Dinuclear Lanthanide(III) Complexes with a Tridentate Schiff-Base Ligand

Abstract: The employment of N-(2-carboxyphenyl)salicylideneimine in 4f metal chemistry has led to two families of dinuclear complexes depending on the lanthanide(III) used. Representative members exhibit interesting magnetic, optical, and catalytic properties.

Cited by 13 publications

References 44 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

Effect of Additives in the Hydroamination/Cyclization of Aminoalkenes Catalyzed by a Binaphtholate Yttrium Catalyst

Trapping an Unexpected/Unprecedented Hexanuclear Ce(III) Hydrolysis Product with Neutral 4‐Amino‐1,2,4‐triazole

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Multifunctionality in Two Families of Dinuclear Lanthanide(III) Complexes with a Tridentate Schiff-Base Ligand

Abstract: The employment of N-(2-carboxyphenyl)­salicylideneimine in 4f metal chemistry has led to two families of dinuclear complexes depending on the lanthanide­(III) used. Representative members exhibit interesting magnetic, optical, and catalytic properties.

Cited by 13 publications

References 44 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

Effect of Additives in the Hydroamination/Cyclization of Aminoalkenes Catalyzed by a Binaphtholate Yttrium Catalyst

Trapping an Unexpected/Unprecedented Hexanuclear Ce(III) Hydrolysis Product with Neutral 4‐Amino‐1,2,4‐triazole

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Abstract: The employment of N-(2-carboxyphenyl)salicylideneimine in 4f metal chemistry has led to two families of dinuclear complexes depending on the lanthanide(III) used. Representative members exhibit interesting magnetic, optical, and catalytic properties.