Polyhedral Structures with an Odd Number of Vertices: Nine‐Coordinate Metal Compounds

Ruiz‐Martínez, Antonio; Casanova, David; Álvarez, Santiago

doi:10.1002/chem.200701137

Cited by 325 publications

(279 citation statements)

References 67 publications

(103 reference statements)

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“…These coordination geometries are not typical for plutonium since the most prevalent coordination environment for nine-coordinate lanthanides and actinides is a tricapped trigonal prism. 78 However, in this compound six of the oxygen atoms are close to being in a plane. Fig.…”

Section: Plutonium(iii) Boratesmentioning

confidence: 86%

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Recent progress in actinide borate chemistry

et al. 2011

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The use of molten boric acid as a reactive flux for synthesizing actinide borates has been developed in the past two years providing access to a remarkable array of exotic materials with both unusual structures and unprecedented properties.[ThB 5 O 6 (OH) 6 ][BO(OH) 2 ]Á2.5H 2 O possesses a cationic supertetrahedral structure and displays remarkable anion exchange properties with high selectivity for TcO 4 À . Uranyl borates form noncentrosymmetric structures with extraordinarily rich topological relationships. Neptunium borates are often mixed-valent and yield rare examples of compounds with one metal in three different oxidation states. Plutonium borates display new coordination chemistry for trivalent actinides. Finally, americium borates show a dramatic departure from plutonium borates, and there are scant examples of families of actinides compounds that extend past plutonium to examine the bonding of later actinides. There are several grand challenges that this work addresses. The foremost of these challenges is the development of structure-property relationships in transuranium materials. A deep understanding of the materials chemistry of actinides will likely lead to the development of advanced waste forms for radionuclides present in nuclear waste that prevent their transport in the environment. This work may have also uncovered the solubility-limiting phases of actinides in some repositories, and allows for measurements on the stability of these materials.

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Section: Plutonium(iii) Boratesmentioning

confidence: 86%

“…Fig. 10 (a) described as hula-hoop 78 and the ten-coordinate coordination geometry is capped triangular cupola. 79 Both types of coordination geometries are extremely rare in lanthanide and actinide compounds except for the borate system that are now known.…”

Section: Plutonium(iii) Boratesmentioning

confidence: 99%

Recent progress in actinide borate chemistry

et al. 2011

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“…The hydrazone Schiff base ligand provides an N 2 O 2 donor set to each Dy III with a fifth O atom provided by the bridging alkoxide function of the ligand from the second Dy III . This circular environment forms the "hula-hoop" motif first identified in [17,18] for nine coordinated metal ion with six coordination sites in the plan ring and more recently extended to eight coordinated Dy ions with five coordination sites in the plane ring by Tang and co-workers [15]. The coordination sphere is completed by two O atoms from the bidentate OAc-co-ligand above the plane of the ring and an O atom from the coordination solvent (EtOH/MeOH for 1 and H 2 O for 2) below the plane.…”

Section: Molecular Structures Of Compounds 1 Andmentioning

confidence: 87%

Tuning of Hula-Hoop Coordination Geometry in a Dy Dimer

et al. 2016

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Abstract:The reaction of DyCl 3 with hydrazone Schiff base ligands and sodium acetate in the presence of triethylamine (Et 3 N) as base affords two dysprosium dimers: [Dy 2 (HL1) 2 (OAc) 2 (EtOH)(MeOH)] (1) and [Dy 2 (L2) 2 (OAc) 2 (H 2 O) 2 ]¨2MeOH (2). The Dy III ions in complexes 1 and 2 are linked by alkoxo bridges, and display "hula hoop" coordination geometries. Consequently, these two compounds show distinct magnetic properties. Complex 1 behaves as a field-induced single molecule magnet (SMM), while typical SMM behavior was observed for complex 2. In addition, comparison of the structural parameters among similar Dy 2 SMMs with hula hoop-like geometry reveals the significant role played by coordination geometry and magnetic interaction in modulating the relaxation dynamics of SMMs.

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“…At first glance, the fact that the Ln III centers in the isomorphous complexes 1·2MeOH, 2·2MeOH and 4·2MeOH have different coordination geometries (and not consistent CShM values) seems strange. We attribute this to two factors: (i) For a given ligand set of nine donor atoms, the tricapped trigonal prism, capped square antiprism and capped cube polyhedra have comparable energies [48,49] and there exist minimal distortion interconversion paths between them; thus many structures are intermediate between two ideal shapes [48], and (ii) the Ln III -donor atom distances are slightly different due to lanthanide(III) contraction and this can affect the shape. For example, the CShM values of the Dy III center in 4·2MeOH for the spherical capped square antiprism (3.263), spherical-relaxed capped cube (4.016) and tricapped trigonal prism (4.165) are all low and similar (Table S1), and its polyhedron could be equally well described as spherical-relaxed capped cube (a polyhedron that gives the lowest CShM value for the Pr III center in 1·2MeOH, Table S3).…”

Section: Interatomic Distances (å) Amentioning

confidence: 99%

Using the Singly Deprotonated Triethanolamine to Prepare Dinuclear Lanthanide(III) Complexes: Synthesis, Structural Characterization and Magnetic Studies

et al. 2017

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Abstract:The 1:1 reactions between hydrated lanthanide(III) nitrates and triethanolamine (teaH 3 ) in MeOH, in the absence of external bases, have provided access to the dinuclear complexes [Ln 2 (NO 3 ) 4 (teaH 2 ) 2 ] (Ln = Pr, 1; Ln = Gd, 2; Ln = Tb, 3; Ln = Dy, 4; Ln = Ho, 5) containing the singly deprotonated form of the ligand. Use of excess of the ligand in the same solvent gives mononuclear complexes containing the neutral ligand and the representative compound [Pr(NO 3 )(teaH 3 ) 2 ](NO 3 ) 2 (6) was characterized. The structures of the isomorphous complexes 1·2MeOH, 2·2MeOH and 4·2MeOH were solved by single-crystal X-ray crystallography; the other two dinuclear complexes are proposed to be isostructural with 1, 2 and 4 based on elemental analyses, IR spectra and powder XRD patterns. The IR spectra of 1-6 are discussed in terms of structural features of the complexes. The two Ln III atoms in centrosymmetric 1·2MeOH, 2·2MeOH and 4·2MeOH are doubly bridged by the deprotonated oxygen atoms of the two η 1 :η 1 :η 1 :η 2 :µ 2 teaH 2 − ligands. The teaH 2 − nitrogen atom and six terminal oxygen atoms (two from the neutral hydroxyl groups of teaH 2 − and four from two slightly anisobidentate chelating nitrato groups) complete 9-coordination at each 4f-metal center. The coordination geometries of the metal ions are spherical-relaxed capped cubic (1·2MeOH), Johnson tricapped trigonal prismatic (2·2MeOH) and spherical capped square antiprismatic (4·2MeOH). O-H···O H bonds create chains parallel to the a axis. The cation of 6 has crystallographic two fold symmetry and the rotation axis passes through the Pr III atom, the nitrogen atom of the coordinated nitrato group and the non-coordinated oxygen atom of the nitrato ligand. The metal ion is bound to the two η 1 :η 1 :η 1 :η 1 teaH 3 ligands and to one bidentate chelating nitrato group. The 10-coordinate Pr III atom has a sphenocoronal coordination geometry. Several H bonds are responsible for the formation of a 3D architecture in the crystal structure of 6. Complexes 1-6 are new members of a small family of homometallic Ln III complexes containing various forms of triethanolamine as ligands. Dc magnetic susceptibility studies in the 2-300 K range reveal the presence of a weak to moderate intramolecular antiferromagnetic exchange interaction (J = −0.30(2) cm −1 based on the spin HamiltonianĤ = −J(Ŝ Gd1 ·Ŝ Gd1 )) for 2 and probably weak antiferromagnetic exchange interactions within the molecules of 3-5. The antiferromagnetic Gd III ···Gd III interaction in 2 is discussed in terms of known magnetostructural correlations for complexes possessing the {Gd 2 (µ 2 -OR) 2 } 4+ core. Ac magnetic susceptibility measurements in zero dc field for 3-5 do not show frequency dependent out-of-phase signals; this experimental fact is discussed and rationalized for complex 4 in terms of the magnetic anisotropy axis for each Dy III center and the oblate electron density of the metal ion.

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Polyhedral Structures with an Odd Number of Vertices: Nine‐Coordinate Metal Compounds

Cited by 325 publications

References 67 publications

Recent progress in actinide borate chemistry

Recent progress in actinide borate chemistry

Tuning of Hula-Hoop Coordination Geometry in a Dy Dimer

Using the Singly Deprotonated Triethanolamine to Prepare Dinuclear Lanthanide(III) Complexes: Synthesis, Structural Characterization and Magnetic Studies

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