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混合金属铀（VI）碘酸盐：Rb[UO(2)(CrO(4))(IO(3))(H(2)O)]、A(2)[UO(2)(CrO(4))(IO(3))(2)]（A = K、Rb、Cs）和K(2)[UO(2)(MoO(4))(IO(3))(2)]的水热合成、结构及反应活性

Mixed-metal uranium(VI) iodates: hydrothermal syntheses, structures, and reactivity of Rb[UO(2)(CrO(4))(IO(3))(H(2)O)], A(2)[UO(2)(CrO(4))(IO(3))(2)] (A = K, Rb, Cs), and K(2)[UO(2)(MoO(4))(IO(3))(2)].

作者信息

Sykora Richard E, McDaniel Steven M, Wells Daniel M, Albrecht-Schmitt Thomas E

机构信息

Department of Chemistry, Auburn University, Auburn, AL 36849, USA.

出版信息

Inorg Chem. 2002 Oct 7;41(20):5126-32. doi: 10.1021/ic025773y.

DOI:10.1021/ic025773y
PMID:12354046
Abstract

The reactions of the molecular transition metal iodates A[CrO(3)(IO(3))] (A = K, Rb, Cs) with UO(3) under mild hydrothermal conditions provide access to four new, one-dimensional, uranyl chromatoiodates, Rb[UO(2)(CrO(4))(IO(3))(H(2)O)] (1) and A(2)[UO(2)(CrO(4))(IO(3))(2)] (A = K (2), Rb (3), Cs (4)). Under basic conditions, MoO(3), UO(3), and KIO(4) can be reacted to form K(2)[UO(2)(MoO(4))(IO(3))(2)] (5), which is isostructural with 2 and 3. The structure of 1 consists of one-dimensionalUO(2)(CrO(4))(IO(3))(H(2)O) ribbons that contain uranyl moieties bound by bridging chromate and iodate anions as well as a terminal water molecule to create [UO(7)] pentagonal bipyramidal environments around the U(VI) centers. These ribbons are separated from one another by Rb(+) cations. When the iodate content is increased in the hydrothermal reactions, the terminal water molecule is replaced by a monodentate iodate anion to yield 2-4. These ribbons can be further modified by replacing tetrahedral chromate anions with MoO(4)(2)(-) anions to yield isostructural, one-dimensional UO(2)(MoO(4))(IO(3))(2)(-) ribbons. Crystallographic data: 1, triclinic, space group P(-)1, a = 7.3133(5) A, b = 8.0561(6) A, c = 8.4870(6) A, alpha = 88.740(1) degrees, beta = 87.075(1) degrees, gamma = 71.672(1) degrees, Z = 2; 2, monoclinic, space group P2(1)/c, a = 11.1337(5) A, b = 7.2884(4) A, c = 15.5661(7) A, beta = 107.977(1) degrees, Z = 4; 3, monoclinic, space group P2(1)/c, a = 11.3463(6) A, b = 7.3263(4) A, c = 15.9332(8) A, beta = 108.173(1) degrees, Z = 4; 4, monoclinic, space group P2(1)/n, a = 7.3929(5) A, b = 8.1346(6) A, c = 22.126(2) A, beta = 90.647(1) degrees, Z = 4; 5, monoclinic, space group P2(1)/c, a = 11.3717(6) A, b = 7.2903(4) A, c = 15.7122(8) A, beta = 108.167(1) degrees, Z = 4.

摘要

分子过渡金属碘酸盐A[CrO(3)(IO(3))]（A = K、Rb、Cs）在温和水热条件下与UO(3)反应，得到了四种新型一维铀酰铬碘酸盐，Rb[UO(2)(CrO(4))(IO(3))(H(2)O)]（1）和A(2)[UO(2)(CrO(4))(IO(3))(2)]（A = K（2）、Rb（3）、Cs（4））。在碱性条件下，MoO(3)、UO(3)和KIO(4)反应生成K(2)[UO(2)(MoO(4))(IO(3))(2)]（5），它与2和3同构。1的结构由一维UO(2)(CrO(4))(IO(3))(H(2)O)带组成，这些带包含由桥连铬酸根和碘酸根阴离子以及一个端基水分子结合的铀酰部分，在U(VI)中心周围形成[UO(7)]五角双锥环境。这些带被Rb(+)阳离子彼此隔开。当水热反应中碘酸盐含量增加时，端基水分子被单齿碘酸根阴离子取代，生成2 - 4。通过用MoO(4)(2)(-)阴离子取代四面体铬酸根阴离子，这些带可以进一步改性，生成同构的一维UO(2)(MoO(4))(IO(3))(2)(-)带。晶体学数据：1，三斜晶系，空间群P(-)1，a = 7.3133(5) Å，b = 8.0561(6) Å，c = 8.4870(6) Å，α = 88.740(1)°，β = 87.075(1)°，γ = 71.672(1)°，Z = 2；2，单斜晶系，空间群P2(1)/c，a = 11.1337(5) Å，b = 7.2884(4) Å，c = 15.5661(7) Å，β = 107.977(1)°，Z = 4；3，单斜晶系，空间群P2(1)/c，a = 11.3463(6) Å，b = 7.3263(4) Å，c = 15.9332(8) Å，β = 108.173(1)°，Z = 4；4，单斜晶系，空间群P2(1)/n，a = 7.3929(5) Å，b = 8.1346(6) Å，c = 22.126(2) Å，β = 90.647(1)°，Z = 4；5，单斜晶系，空间群P2(1)/c，a = 11.3717(6) Å，b = 7.2903(4) Å，c = 15.7122(8) Å，β = 108.167(1)°，Z = 4。

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