Reactions of UCl4 withtBu-Calix[4, 5, and 6]arenes: The First “Non-Uranyl” Calixarene Complexes of Uranium

Leverd, Pascal C.; Nierlich, Martine

doi:10.1002/1099-0682(200008)2000:8<1733::aid-ejic1733>3.0.co;2-l

Cited by 36 publications

(16 citation statements)

References 37 publications

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“…These values are typical for tetravalent uranium bonded to terminal chloride anions and were found in other compounds. [40][41][42][43][44][45][46][47] Bond valence calculations 48 for uranium gave values of 4.01 (1) and 4.08 (2), which are in good agreement with the oxidation state +4. The resulting coordination polyhedron around the uranium cation is a distorted tricapped trigonal prism, UO c 6 O f 2 Cl (' c ': carboxylate; ' f ': formamide), with two carboxyl oxygens of chelating carboxylate groups and one oxygen from formamide function capping each of its square faces.…”

Section: Structures Descriptionsupporting

confidence: 52%

Coordination polymers of uranium(iv) terephthalates

et al. 2015

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A series of tetravalent uranium terephthalates has been solvothermally synthesized in the solvent N,N-dimethylformamide (DMF) at temperature 100-150 °C with different water amounts. Composition diagrams have been determined for the U(4+) metallic cation in the presence of terephthalic acid, and their crystal structures revealed the occurrence of two- or three-dimensional coordination polymers. In the absence of water, a mixture of two polytypes T-U(2)Cl(2)(bdc)(3)(DMF)(4) (1) and M-U(2)Cl(2)(bdc)(3)(DMF)(4) (2) has been identified at low temperature (100-110 °C) for bdc/U = 1-4 (bdc = terephthalate linker). Their structures are built up from isolated uranium centers in nine-fold coordination, surrounded by 6 carboxyl oxygen atoms, 2 oxygen atoms coming from DMF molecules and one chlorine atom. The uranium cations are linked to each other through the bdc ligand in order to generate a 3D framework. By increasing the temperature (130-150 °C), a layered like compound has been isolated, U(2)(bdc)(4)(DMF)(4) (3). It is composed of discrete actinide centers in ten-fold coordination, with 8 carboxyl oxygen atoms and 2 oxygen atoms from DMF molecules. The connection of the UO10 units with the bdc linkers generates 2D sheets. When a controlled amount of water is added to the reaction medium, the crystallization of the UiO-66-like U(6)O(4)(OH)(4)(H(2)O)(6)(bdc)(6)·10DMF solid (containing a hexanuclear sub-unit) is observed for temperature 110-120 °C and the H(2)O/U molar ratio in the range of 2-10. At higher temperature (140-150 °C), a distinct phase appeared, U(2)O(2)(bdc)(2)(DMF) (4), which consists of infinite chains of uranium centers, linked to each other via the bdc ligands. Higher water contents led to the formation of urania UO(2).

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Section: Structures Descriptionsupporting

confidence: 52%

Coordination polymers of uranium(iv) terephthalates

et al. 2015

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“…Using similar chemistry, bimetallic mixed-valent uranium(IV/V) calixarene complexes have also been prepared. 72,73 (18)…”

Section: ð15þmentioning

confidence: 99%

Pentavalent uranium chemistry—synthetic pursuit of a rare oxidation state

2009

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“…196 The first non-uranyl calixarene complexes of uranium have been reported. 197 [U(tpa)I 3 (py)] features 8-coordinate uranium, like the lanthanum analogue. 79 Reaction of [UI 3 (thf) 4 ] with Mentb permits displacement of the iodides and affords [U(Mentb) 2 ]I 3 •3py, also eight-coordinate.…”

Section: Binary Compounds and Complexesmentioning

confidence: 99%

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Cotton¹

2001

Annu. Rep. Prog. Chem., Sect. A

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Reactions of UCl4 withtBu-Calix[4, 5, and 6]arenes: The First “Non-Uranyl” Calixarene Complexes of Uranium

Cited by 36 publications

References 37 publications

Coordination polymers of uranium(iv) terephthalates

Coordination polymers of uranium(iv) terephthalates

Pentavalent uranium chemistry—synthetic pursuit of a rare oxidation state

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