TY - JOUR
T1 - The synthesis, structural, and spectroscopic characterization of uranium(IV) perrhenate complexes
AU - John, Gordon H.
AU - May, Iain
AU - Sharrad, Clint A.
AU - Sutton, Andrew D.
AU - Collison, David
AU - Helliwell, Madeleine
AU - Sarsfield, Mark J.
PY - 2005/10/17
Y1 - 2005/10/17
N2 - We report the synthesis, structural, and spectroscopic characterization of a series of uranium(IV)-perrhenato complexes. Three isostructural complexes with general formula [U(ReO4)4(L)4] (where L = tri-n-butylphosphine oxide/TBPO (2), triethyl phosphate/TEP (3), or tri-iso-butyl phosphate/TiBP (4)), have been synthesized, both through the photoreduction of ethanolic {UO2}2+ solutions and also via a novel UIV starting material, U(ReO4) 4·5H2O (1). Compound 1 has also been used in the preparation of [U(ReO4)4(TPPO)3(CH 3CN)]·2CH3CN (5) and [U(ReO4)- (DPPMO2)3(OH)][ReO4]2· 2CH3CN (6), where TPPO represents triphenylphosphine oxide and DPPMO2 represents bis(diphenylphosphino)methane dioxide. All six complexes have been spectroscopically characterized using NMR, UV-vis-NIR, and IR techniques, with 2, 3, 5, and 6 also fully structurally characterized. The U atoms in compounds 2-6 all exhibit eight-coordinate geometry with up to four perrhenate groups in addition to three (DPPMO2 and TPPO) or four (TEP, TiBP, TBPO) coordinated organic ligands. In the case of compounds 5 and 6, the coordination of eight ligands to the UIV center is completed by the binding of a solvent molecule (CH3CN) and OH-, respectively. Solid-state physical analysis (elemental and thermogravimetric) and infrared spectroscopy are in agreement with the structural studies. The crystallographic data suggest that the strength of the UIV-O-donor ligand bonds decreases across the series R3PO > [ReO4]-> (RO)3PO. Solution-state IR and 31P NMR spectroscopy appear to be in agreement with these solid-state results.
AB - We report the synthesis, structural, and spectroscopic characterization of a series of uranium(IV)-perrhenato complexes. Three isostructural complexes with general formula [U(ReO4)4(L)4] (where L = tri-n-butylphosphine oxide/TBPO (2), triethyl phosphate/TEP (3), or tri-iso-butyl phosphate/TiBP (4)), have been synthesized, both through the photoreduction of ethanolic {UO2}2+ solutions and also via a novel UIV starting material, U(ReO4) 4·5H2O (1). Compound 1 has also been used in the preparation of [U(ReO4)4(TPPO)3(CH 3CN)]·2CH3CN (5) and [U(ReO4)- (DPPMO2)3(OH)][ReO4]2· 2CH3CN (6), where TPPO represents triphenylphosphine oxide and DPPMO2 represents bis(diphenylphosphino)methane dioxide. All six complexes have been spectroscopically characterized using NMR, UV-vis-NIR, and IR techniques, with 2, 3, 5, and 6 also fully structurally characterized. The U atoms in compounds 2-6 all exhibit eight-coordinate geometry with up to four perrhenate groups in addition to three (DPPMO2 and TPPO) or four (TEP, TiBP, TBPO) coordinated organic ligands. In the case of compounds 5 and 6, the coordination of eight ligands to the UIV center is completed by the binding of a solvent molecule (CH3CN) and OH-, respectively. Solid-state physical analysis (elemental and thermogravimetric) and infrared spectroscopy are in agreement with the structural studies. The crystallographic data suggest that the strength of the UIV-O-donor ligand bonds decreases across the series R3PO > [ReO4]-> (RO)3PO. Solution-state IR and 31P NMR spectroscopy appear to be in agreement with these solid-state results.
UR - http://www.scopus.com/inward/record.url?scp=27544509076&partnerID=8YFLogxK
U2 - 10.1021/ic0507971
DO - 10.1021/ic0507971
M3 - Article
AN - SCOPUS:27544509076
SN - 0020-1669
VL - 44
SP - 7606
EP - 7615
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 21
ER -