A new structural family of heteropolytungstate lacunary complexes with the uranyl, UO22+, cation

Andrew J. Gaunt; Iain May; Roy Copping; Anand I. Bhatt; David Collison; O. Danny Fox; K. Travis Holman; Michael T. Pope

doi:10.1039/b302955g

A new structural family of heteropolytungstate lacunary complexes with the uranyl, UO₂²⁺, cation

Andrew J. Gaunt, Iain May, Roy Copping, Anand I. Bhatt, David Collison, O. Danny Fox, K. Travis Holman, Michael T. Pope

Research output: Contribution to journal › Article › peer-review

80 Scopus citations

Abstract

The reaction of UO2₂²⁺ with the trivacant lacunary polyoxometalate anions, [SbW₉O₃₃]^9- and [TeW₉O₃₃]^8-, yields the novel isostructural complexes [(UO₂)₂(H₂O)₂(SbW ₉O₃₃)₂]^14- (1) and [(UO ₂)₂(H₂O)₂(TeW₉O ₃₃)₂]^12- (2), respectively. The complex anions contain two [XW₉O₃₃]^n- (X = Sb^III or Te^IV) anions linked by two UO₂²⁺ cations. Each uranyl moiety bonds to two unsaturated oxygen atoms of each lacunary anion in the complex. Each [XW₉O₃₃]^n- anion has six unsaturated oxygen atoms meaning that in 1 and 2 each [XW₉O ₃₃]^n- anion has two unsaturated oxygen atoms which remain uncoordinated to uranium with the result being the formation of an 'open' sandwich structure. The fact that a third UO₂²⁺ cation is not coordinated to form a 'closed' sandwich structure (as is observed for first row d-block transition metals) is attributed to the steric hindrance of the axial 'yl' oxygen atoms of the uranyl group. The products, prepared as NH ₄⁺ salts, have been characterised by single crystal X-ray diffraction, elemental analysis, TGA analysis, IR, Raman and UV/vis spectroscopy, which indicate that the O donor atoms of the lacunary heteropolytungstate anions are strongly coordinating to U(VI) in the equatorial plane, weakening the uranyl U-O axial bonds.

Original language	English
Pages (from-to)	3009-3014
Number of pages	6
Journal	Dalton Transactions
Issue number	15
DOIs	https://doi.org/10.1039/b302955g
State	Published - Aug 7 2003
Externally published	Yes

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@article{0ba0e50b0fa74808b492972b131b48f8,

title = "A new structural family of heteropolytungstate lacunary complexes with the uranyl, UO22+, cation",

abstract = "The reaction of UO222+ with the trivacant lacunary polyoxometalate anions, [SbW9O33]9- and [TeW9O33]8-, yields the novel isostructural complexes [(UO2)2(H2O)2(SbW 9O33)2]14- (1) and [(UO 2)2(H2O)2(TeW9O 33)2]12- (2), respectively. The complex anions contain two [XW9O33]n- (X = SbIII or TeIV) anions linked by two UO22+ cations. Each uranyl moiety bonds to two unsaturated oxygen atoms of each lacunary anion in the complex. Each [XW9O33]n- anion has six unsaturated oxygen atoms meaning that in 1 and 2 each [XW9O 33]n- anion has two unsaturated oxygen atoms which remain uncoordinated to uranium with the result being the formation of an 'open' sandwich structure. The fact that a third UO22+ cation is not coordinated to form a 'closed' sandwich structure (as is observed for first row d-block transition metals) is attributed to the steric hindrance of the axial 'yl' oxygen atoms of the uranyl group. The products, prepared as NH 4+ salts, have been characterised by single crystal X-ray diffraction, elemental analysis, TGA analysis, IR, Raman and UV/vis spectroscopy, which indicate that the O donor atoms of the lacunary heteropolytungstate anions are strongly coordinating to U(VI) in the equatorial plane, weakening the uranyl U-O axial bonds.",

author = "Gaunt, {Andrew J.} and Iain May and Roy Copping and Bhatt, {Anand I.} and David Collison and Fox, {O. Danny} and Holman, {K. Travis} and Pope, {Michael T.}",

year = "2003",

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doi = "10.1039/b302955g",

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T1 - A new structural family of heteropolytungstate lacunary complexes with the uranyl, UO22+, cation

AU - Gaunt, Andrew J.

AU - May, Iain

AU - Copping, Roy

AU - Bhatt, Anand I.

AU - Collison, David

AU - Fox, O. Danny

AU - Holman, K. Travis

AU - Pope, Michael T.

PY - 2003/8/7

Y1 - 2003/8/7

N2 - The reaction of UO222+ with the trivacant lacunary polyoxometalate anions, [SbW9O33]9- and [TeW9O33]8-, yields the novel isostructural complexes [(UO2)2(H2O)2(SbW 9O33)2]14- (1) and [(UO 2)2(H2O)2(TeW9O 33)2]12- (2), respectively. The complex anions contain two [XW9O33]n- (X = SbIII or TeIV) anions linked by two UO22+ cations. Each uranyl moiety bonds to two unsaturated oxygen atoms of each lacunary anion in the complex. Each [XW9O33]n- anion has six unsaturated oxygen atoms meaning that in 1 and 2 each [XW9O 33]n- anion has two unsaturated oxygen atoms which remain uncoordinated to uranium with the result being the formation of an 'open' sandwich structure. The fact that a third UO22+ cation is not coordinated to form a 'closed' sandwich structure (as is observed for first row d-block transition metals) is attributed to the steric hindrance of the axial 'yl' oxygen atoms of the uranyl group. The products, prepared as NH 4+ salts, have been characterised by single crystal X-ray diffraction, elemental analysis, TGA analysis, IR, Raman and UV/vis spectroscopy, which indicate that the O donor atoms of the lacunary heteropolytungstate anions are strongly coordinating to U(VI) in the equatorial plane, weakening the uranyl U-O axial bonds.

AB - The reaction of UO222+ with the trivacant lacunary polyoxometalate anions, [SbW9O33]9- and [TeW9O33]8-, yields the novel isostructural complexes [(UO2)2(H2O)2(SbW 9O33)2]14- (1) and [(UO 2)2(H2O)2(TeW9O 33)2]12- (2), respectively. The complex anions contain two [XW9O33]n- (X = SbIII or TeIV) anions linked by two UO22+ cations. Each uranyl moiety bonds to two unsaturated oxygen atoms of each lacunary anion in the complex. Each [XW9O33]n- anion has six unsaturated oxygen atoms meaning that in 1 and 2 each [XW9O 33]n- anion has two unsaturated oxygen atoms which remain uncoordinated to uranium with the result being the formation of an 'open' sandwich structure. The fact that a third UO22+ cation is not coordinated to form a 'closed' sandwich structure (as is observed for first row d-block transition metals) is attributed to the steric hindrance of the axial 'yl' oxygen atoms of the uranyl group. The products, prepared as NH 4+ salts, have been characterised by single crystal X-ray diffraction, elemental analysis, TGA analysis, IR, Raman and UV/vis spectroscopy, which indicate that the O donor atoms of the lacunary heteropolytungstate anions are strongly coordinating to U(VI) in the equatorial plane, weakening the uranyl U-O axial bonds.

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U2 - 10.1039/b302955g

DO - 10.1039/b302955g

M3 - Article

AN - SCOPUS:12344259743

SN - 1477-9226

SP - 3009

EP - 3014

JO - Dalton Transactions

JF - Dalton Transactions

IS - 15

ER -

A new structural family of heteropolytungstate lacunary complexes with the uranyl, UO₂²⁺, cation

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