The School of Chemical Sciences, University of Illinois at Urbana-Champaign, 600 South Mathews Avenue, Urbana, Illinois 61801, USA.
Inorg Chem. 2010 Jun 7;49(11):5157-66. doi: 10.1021/ic100290j.
The reaction of UCl(4) with sodium N,N-dimethylaminodiboranate, Na(H(3)BNMe(2)BH(3)), in diethyl ether affords the uranium(III) product U(H(3)BNMe(2)BH(3))(3), which has been crystallized as two different structural isomers from pentane and toluene, respectively. The isomer crystallized from pentane is a polymer in which each uranium center is bonded to three chelating H(3)BNMe(2)BH(3)(-) (DMADB) ligands and to one hydrogen atom from a neighboring molecule so as to form an intermolecular B-H-U bridge; each uranium center is coordinated to 13 hydrogen atoms. The isomer crystallized from toluene is also polymeric, but the uranium atoms are coordinated by two chelating DMADB ligands and two bridging DMADB ligands bound in a U(kappa(3)H-H(3)BNMe(2)BH(3)-kappa(3)H)U fashion, so that each uranium atom is 14-coordinate. When the reaction of UCl(4) with Na(H(3)BNMe(2)BH(3)) is conducted in tetrahydrofuran (thf) or 1,2-dimethoxyethane (dme), the adducts U(H(3)BNMe(2)BH(3))(3)(thf) and U(H(3)BNMe(2)BH(3))(3)(dme) are obtained. The rate of reduction from U(IV) to U(III) is correlated with the donor ability of the solvent, the relative rates being Et(2)O > thf > dme. The addition of trimethylphosphine to U(H(3)BNMe(2)BH(3))(3)(thf) generates U(H(3)BNMe(2)BH(3))(3)(PMe(3))(2). This compound slowly decomposes at room temperature over several months to yield the new borane PMe(3)BH(2)NMe(2)BH(3), mu-(N,N-dimethylamido)pentahydro(trimethylphosphine)diboron. Single crystal X-ray diffraction studies, (1)H and (11)B NMR spectra, IR data, and field ionization mass spectra for the uranium complexes are reported.
四氯化铀（UCl(4)）与二乙基醚中的钠 N,N-二甲基氨基二硼酸盐，Na(H(3)BNMe(2)BH(3))，反应得到铀(III)产物 U(H(3)BNMe(2)BH(3))(3)，分别从戊烷和甲苯中结晶得到两种不同结构的异构体。从戊烷中结晶的异构体是一种聚合物，其中每个铀中心与三个螯合 H(3)BNMe(2)BH(3)(-)（DMADB）配体和一个来自相邻分子的氢原子键合，形成分子间 B-H-U 桥；每个铀中心与 13 个氢原子配位。从甲苯中结晶的异构体也是聚合物，但铀原子由两个螯合 DMADB 配体和两个桥联 DMADB 配体配位，形成 U(kappa(3)H-H(3)BNMe(2)BH(3)-kappa(3)H)U 方式，从而使每个铀原子为 14 配位。当 UCl(4)与 Na(H(3)BNMe(2)BH(3))在四氢呋喃（thf）或 1,2-二甲氧基乙烷（dme）中反应时，得到加成物 U(H(3)BNMe(2)BH(3))(3)(thf)和 U(H(3)BNMe(2)BH(3))(3)(dme)。从 U(IV)还原为 U(III)的速率与溶剂的供电子能力有关，相对速率为 Et(2)O > thf > dme。向 U(H(3)BNMe(2)BH(3))(3)(thf)中添加三甲基膦生成 U(H(3)BNMe(2)BH(3))(3)(PMe(3))(2)。该化合物在室温下缓慢分解数月，生成新的硼烷 PMe(3)BH(2)NMe(2)BH(3)，μ-(N,N-二甲基酰胺)五氢（三甲基膦）二硼。报道了铀配合物的单晶 X 射线衍射研究、(1)H 和 (11)B NMR 谱、IR 数据和场电离质谱。
