DITHIOPHOSPHINATE COMPLEXES OF THE UO22+ ION CONTAINING A COORDINATED WATER MOLECULE SOLID STATE STRUCTURES AND STEREOCHEMICAL RIGIDITY IN SOLUTION

摘要

Complexes of formula [UO2{S2P(Pr-i)(2)}(2).H2O] have been isolated either unsolvated (I) or as acetonitrile solvates (II and III). They have been characterized by X-ray crystallography and NMR spectroscopy. The UO3S4 core deformation from ideal geometry varies widely in the solid state and is shown to become stereochemically rigid at moderately low temperature in solution. Crystal data for complex I:[UO2{S2P(Pr-i)(2)}(2).H2O], C12H30O3P2S4U, Mr=650.61. monoclinic, P2(1)/c, a=8.685(1), b=12.445(1), c=21.536(3) Angstrom, beta=94.78(1)degrees V=2320(1) Angstrom(3), Z=4, D-x=1.86 g cm(-3), R=0.028; complex II: [UO2{S2P(Pr-i)(2)}(2).H2O].MeCN, C14H33NO3P2S4U, Mr=691.66, orthorhombic, Pbca, a=28.831(3), b=16.536(2), c=10.801(1) Angstrom, V=5149(2) Angstrom(3), Z=8, D-x=1.78 g cm(-3), R=0.042; complex III: [UO2{S2P(Pr-i)(2)}(2).H2O].MeCN, C14H33NO3P2S4 U, Mr=691.66, monoclinic, P2(1)/c, a=14.626(2), b=16.468(2), c=10.873(2) Angstrom, beta=100.29(1)degrees, V=2577(i) Angstrom(3), Z=4, D-x=1.78 g cm(-3), R=0.054. [References: 17]