Karimova Oxana V, Burns Peter C
Department of Civil Engineering and Geological Sciences, 156 Fitzpatrick Hall, University of Notre Dame, Notre Dame, Indiana 46556, USA.
Inorg Chem. 2007 Nov 26;46(24):10108-13. doi: 10.1021/ic701128b. Epub 2007 Oct 31.
Three uranyl perrhenates have been synthesized, and their structures have been determined. (UO2)2(ReO4)4(H2O)3 (1) is triclinic, space group P, a=5.2771(7), b=13.100(2), c=15.476(2) A, alpha=107.180(2), beta=99.131(3), gamma=94.114(2) degrees, V=1001.12 A3, Z=2. (UO2)4(ReO4)2O(OH)4(H2O)75 (2) is also triclinic, space group P, a=7.884(1), b=11.443(2), c=16.976(2) A, alpha=83.195(4), beta=89.387(4), gamma=85.289(4) degrees, V=1515.70 A3, Z=2. Na(UO2)(ReO4)3(H2O)2 (3) is monoclinic, space group C2/m, a=12.311(3), b=22.651(6), c=5.490(1) A, beta=109.366(6) degrees, V=1444.24 A3, Z=4. These compounds are the first structurally characterized uranyl perrhenates that do not contain organic ligands. In each structure, perrhenate groups coordinate uranyl ions at the equatorial vertices of pentagonal bipyramids. 1 contains complex chains of uranyl pentagonal bipyramids that are bridged by vertex sharing with perrhenate groups. The structural units in 2 and 3 consist of three novel finite clusters that include the coordination of uranyl ions with perrhenate. In general, weakly coordinating ligands such as perchlorate, perrhenate, and pertechnetate are assumed not to form stable complexes with uranyl in solutions or solids. The current findings, together with other recently reported studies, indicate each of these ligands can coordinate uranyl, and novel structure types result.
已合成三种高铼酸铀酰，并确定了它们的结构。(UO2)2(ReO4)4(H2O)3（1）为三斜晶系，空间群P，a = 5.2771(7)，b = 13.100(2)，c = 15.476(2) Å，α = 107.180(2)，β = 99.131(3)，γ = 94.114(2)°，V = 1001.12 Å3，Z = 2。(UO2)4(ReO4)2O(OH)4(H2O)75（2）也是三斜晶系，空间群P，a = 7.884(1)，b = 11.443(2)，c = 16.976(2) Å，α = 83.195(4)，β = 89.387(4)，γ = 85.289(4)°，V = 1515.70 Å3，Z = 2。Na(UO2)(ReO4)3(H2O)2（3）为单斜晶系，空间群C2/m，a = 12.311(3)，b = 22.651(6)，c = 5.490(1) Å，β = 109.366(6)°，V = 1444.24 Å3，Z = 4。这些化合物是首批结构表征的不含有机配体的高铼酸铀酰。在每个结构中，高铼酸根离子在五角双锥的赤道顶点处与铀酰离子配位。1包含由铀酰五角双锥通过与高铼酸根离子共用顶点连接而成的复杂链。2和3中的结构单元由三个新颖的有限簇组成，其中包括铀酰离子与高铼酸根的配位。一般认为，诸如高氯酸根、高铼酸根和高锝酸根等弱配位配体在溶液或固体中不会与铀酰形成稳定的配合物。目前的研究结果与最近报道的其他研究一起表明，这些配体中的每一种都可以与铀酰配位，并产生新颖的结构类型。
