已经开发了几种新的合成途径,可以达到空间拥挤的(C 5 Me 5)3 U配合物。(C 5我5)3 U可以通过[(C(a)的反应而制备的5我5)2 UH 2 ] 2与tetramethylfulvene,(B)还原(C的5我5)2与(C铅5我5)2 UH(DMPE),(c)[(C 5 Me 5)2 U(L)] +(L = THF,DMPE)与K(18-crown-6)(C5 Me 5),和(d)[(C 5 Me 5)2 U] [BPh 4 ]与KC 5 Me 5的反应。(C 5 Me 5)2 UH(DMPE)与C 8 H 8的反应形成了(C 5 Me 5)3 U / C 8 H 8反应的产物,[(C 8 H 8)(C 5 Me 5 ] U] 2(C 8 H 8)。(C的X射线晶体结构报告了本研究中使用的5 Me 5)2 U [N(SiMe 3)2 ]和[(C 5 Me 5)2 U] [BPh
Tuning the Oxidation State, Nuclearity, and Chemistry of Uranium Hydrides with Phenylsilane and Temperature: The Case of the Classic Uranium(III) Hydride Complex [(C<sub>5</sub>Me<sub>5</sub>)<sub>2</sub>U(μ-H)]<sub>2</sub>
作者:Justin K. Pagano、Jacquelyn M. Dorhout、Kenneth R. Czerwinski、David E. Morris、Brian L. Scott、Rory Waterman、Jaqueline L. Kiplinger
DOI:10.1021/acs.organomet.6b00091
日期:2016.3.14
This work demonstrates that the oxidation state and chemistry of uranium hydrides can be tuned with temperature and the stoichiometry of phenylsilane. The trivalent uranium hydride [(C5Me5)(2)UH](x) (5) was found to be comprised of an equilibrium mixture of U(III) hydrides in solution at ambient temperature. A single U(III) species can be selectively prepared by treating (C5Me5)(2)UMe2 (4) with 2 equiv of phenylsilane at 50 degrees C. The U(III) system is a potent reducing agent and displayed chemistry distinct from the U(IV) system [(C5Me5)(2)U(H)(-H)](2) (2), which was harnessed to prepare a variety of organometallic complexes, including (C5Me5)(2)U(dmpe)(H) (6), and the novel uranium(IV) metallacyclopentadiene complex (C5Me5)(2)U(C4Me4) (11)