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Crystal structures of metallocene complexes with uranium-germanium bonds.

ABSTRACT: The first structural examples of complexes with uranium-germanium bonds are presented, namely, bis-[3,5-bis-(tri-fluoro-meth-yl)phenyl-2κC ¹](hydrido-2κH)(iodido-1κI)bis-[1,1(η⁵)-penta-methyl-cyclo-penta-dien-yl]germaniumuranium(Ge-U), [GeU(C₁₀H₁₅)₂(C₈H₃F₆)₂HI], and bis-[3,5-bis-(tri-fluoro-meth-yl)phenyl-2κC ¹](fluorido-1κI)(hydrido-2κH)bis-[1,1(η⁵)-penta-methyl-cyclo-penta-dien-yl]germaniumuranium(Ge-U), [GeU(C₁₀H₁₅)₂(C₈H₃F₆)₂FH]. The two complexes both have a long U-Ge bond [distances of 3.0428 (7) and 3.0524 (7) Å].

SUBMITTER: Tarlton ML

PROVIDER: S-EPMC8647732 | biostudies-literature | 2021 Dec

REPOSITORIES: biostudies-literature

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Crystal structures of metallocene complexes with uranium-germanium bonds.

Tarlton Michael L ML Kelley Steven P SP Walensky Justin R JR

Acta crystallographica. Section E, Crystallographic communications 20211109 Pt 12

The first structural examples of complexes with uranium-germanium bonds are presented, namely, bis-[3,5-bis-(tri-fluoro-meth-yl)phenyl-2κC 1](hydrido-2κH)(iodido-1κI)bis-[1,1(η5)-penta-methyl-cyclo-penta-dien-yl]germaniumuranium(Ge-U), [GeU(C10H15)2(C8H3F6)2HI], and bis-[3,5-bis-(tri-fluoro-meth-yl)phenyl-2κC 1](fluorido-1κI)(hydrido-2κ ...[more]

PMID: 34925893

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Project description:The three isomorphous [3.3.1] metallacryptate complexes bis-(pyridinium) di-aqua-dipyridine-hexa-kis-[μ3-salicyl-hydroximato(3-)]bis-[μ2-salicyl-hydroxim-ato(1-)]hexa-aluminiumgadolinium-pyridine-water (1/7.396/1), (C5H6N)2[GdAl6(C7H6NO3)2(C7H4NO3)7(C5H5N)1.855(H2O)2]·7.396C5H5N·H2O or [Hpy]2[GdAl6(H2shi)2(shi)7(py)1.855(H2O)2]·7.396py·H2O, 1, bis-(pyridinium) di-aqua-dipyridine-hexa-kis-[μ3-salicyl-hydroximato(3-)]bis-[μ2-salicyl-hydroxim-ato(1-)]hexa-aluminiumdysprosium-pyridine-water (1/7.429/1), (C5H6N)2[DyAl6(C7H6NO3)2(C7H4NO3)7(C5H5N)1.855(H2O)2]·7.429C5H5N·H2O or [Hpy]2[DyAl6(H2shi)2(shi)7(py)1.891(H2O)2]·7.429py·H2O, 2, and bis-(pyrid-in-ium) di-aqua-dipyridine-hexa-kis-[μ3-salicyl-hydroximato(3-)]bis-[μ2-salicyl-hydrox-imato(1-)]hexa-aluminiumytterbium-pyridine-water (1/7.386/1), (C5H6N)2[YbAl6(C7H6NO3)2(C7H4NO3)7(C5H5N)1.855(H2O)2]·7.429C5H5N·H2O or [Hpy]2[YbAl6(H2shi)2(shi)7(py)1.818(H2O)2]·7.386py·H2O, 3, where Hpy+ is pyridinium, shi3- is salicyl-hydroximate, and py is pyridine, consist of an aluminium-based metallacryptand that captures an Ln III ion in the central cavity. The metallacryptand portions are comprised of an Al-N-O repeat unit; thus, they can be considered three-dimensional metallacrowns. The encapsulated Ln III ions are nine-coordinate with a spherical capped-square-anti-prism geometry, while the six AlIII ions are all octa-hedral. Four of the AlIII ions are chiral centers with 2 Δ and 2 Λ stereoconfigurations. The remaining two AlIII ions have trans chelate rings from two different shi3- ligands. For 1-3, a section of the main mol-ecule is disordered induced by the presence or absence of a pyridine ligand coordinated to one of the AlIII ions. In the absence of the pyridine moiety, an H2shi- ligand moves into the space otherwise occupied by the pyridine and the phenol oxygen atom coordinates to the AlIII ion. The movement of the H2shi- ligand induces movement for the Ln III ion, for another AlIII ion that also binds the same H2shi- ligand, and for one of the shi3- ligands coordinated to the latter AlIII ion. For 1-3 the occupancy ratio of the metallacryptand portions refined to 0.8550 (13):0.1450 (13), to 0.8909 (13):0.1091 (13), and to 0.8181 (14):0.1819 (14), respectively.

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Crystal structures of metallocene complexes with uranium-germanium bonds.

Publications

Crystal structures of metallocene complexes with uranium-germanium bonds.

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