重二卤化双氧铀（VI）的合成与表征

Synthesis and characterization of heavier dioxouranium(VI) dihalides.

作者信息

Crawford Margaret-Jane, Ellern Arkady, Karaghiosoff Konstantin, Mayer Peter, Nöth Heinrich, Suter Max

机构信息

Department of Chemistry and Biochemistry, Ludwig-Maximilians University, Butenandtstrasse 5-13 (Haus D), D-81377, Munich, Germany.

出版信息

Inorg Chem. 2004 Nov 1;43(22):7120-6. doi: 10.1021/ic0354926.

DOI:10.1021/ic0354926

PMID:15500350

Abstract

The synthesis and characterization of the dioxouranium(VI) dibromide and iodide hydrates, UO(2)Br(2)x3H(2)O (1), UO(2)Br(2)(OH(2))(2) (2), and UO(2)I(2)x2H(2)Ox4Et(2)O (3), are reported. Moreover, adducts of UO(2)I(2) and UO(2)Br(2) with large, bulky OP(NMe(2))(3) and OPPh(3) ligands such as UO(2)I(2)(OP(NMe(2))(3))(2) (4), UO(2)Br(2)(OP(NMe(2))(3))(2) (5), and UO(2)I(2)(OPPh(3))(2)(6) are discussed. The structures of the following compounds were determined using single-crystal X-ray diffraction techniques: (1) monoclinic, P2(1)/c, a = 9.7376(8) A, b = 6.5471(5) A, c = 12.817(1) A, beta = 94.104(1) degrees , V = 815.0(1) A(3), Z = 4; (2) monoclinic, P2(1)/c, a = 6.0568(7) A, b = 10.5117(9) A, c = 10.362(1) A, beta = 99.62(1) degrees , V = 650.5(1) A(3), Z = 2; (4) tetragonal, P4(1)2(1)2, a = 10.6519(3) A, b = 10.6519(3) A, c = 24.0758(6) A, V = 2731.7(1) A(3), Z = 4; (5) tetragonal, P4(1)2(1)2, a = 10.4645(1) A, b = 10.4645(1) A, c = 23.7805(3) A, V = 2604.10(5) A(3), Z = 4, and (6) monoclinic, P2(1)/c, a = 9.6543(1) A, b = 18.8968(3) A, c = 10.9042(2) A, beta =115.2134(5) degrees , V = 1783.01(5) A(3), Z = 2. Whereas 1 and 2 are the first UO(2)Br(2) hydrates and the last missing members of the UO(2)X(2) hydrate (X = Cl --> I) series to be structurally characterized, 4 and 6 contain room-temperature stable U(VI)-I bonds with 4 being the first structurally characterized room temperature stable U(VI)-I compound which can be conveniently prepared on a gram scale in quantitative yield. The synthesis and characterization of 5 using an analogous halogen exchange reaction to that used for the preparation of 4 is also reported.

摘要

报道了二溴化二氧铀（VI）水合物、二碘化二氧铀（VI）水合物UO₂Br₂·3H₂O（1）、[UO₂Br₂(OH₂)₂]₂（2）和UO₂I₂·2H₂O·4Et₂O（3）的合成与表征。此外，还讨论了UO₂I₂和UO₂Br₂与大体积的OP(NMe₂)₃和OPPh₃配体形成的加合物，如UO₂I₂(OP(NMe₂)₃)₂（4）、UO₂Br₂(OP(NMe₂)₃)₂（5）和UO₂I₂(OPPh₃)₂（6）。使用单晶X射线衍射技术测定了以下化合物的结构：（1）单斜晶系，P2(1)/c，a = 9.7376(8) Å，b = 6.5471(5) Å，c = 12.817(1) Å，β = 94.104(1)°，V = 815.0(1) Å³，Z = 4；（2）单斜晶系，P2(1)/c，a = 6.0568(7) Å，b = 10.5117(9) Å，c = 10.362(1) Å，β = 99.62(1)°，V = 650.5(1) Å³，Z = 2；（4）四方晶系，P4(1)2(1)2，a = 10.6519(3) Å，b = 10.6519(3) Å，c = 24.0758(6) Å，V = 2731.7(1) Å³，Z = 4；（5）四方晶系，P4(1)2(1)2，a = 10.4645(1) Å，b = 10.4645(1) Å，c = 23.7805(3) Å，V = 2604.10(5) Å³，Z = 4，以及（6）单斜晶系，P2(1)/c，a = 9.6543(1) Å，b = 18.8968(3) Å，c = 10.9042(2) Å，β =115.2134(5)°，V = 1783.01(5) Å³，Z = 2。1和2是首个经结构表征的UO₂Br₂水合物，也是UO₂X₂水合物（X = Cl→I）系列中最后缺失的成员，而4和6含有室温稳定的U(VI)-I键，4是首个经结构表征的室温稳定U(VI)-I化合物，可方便地以克级规模定量制备。还报道了使用与制备4类似的卤交换反应合成和表征5的过程。