Kent Greggory T, Yu Xiaojuan, Pauly Christophe, Wu Guang, Autschbach Jochen, Hayton Trevor W
Department of Chemistry and Biochemistry, University of California-Santa Barbara, Santa Barbara, California 93106, United States.
Department of Chemistry, University at Buffalo, State University of New York, Buffalo, New York 14260, United States.
Inorg Chem. 2021 Oct 18;60(20):15413-15420. doi: 10.1021/acs.inorgchem.1c02064. Epub 2021 Sep 29.
The reaction of [AnCl(NR)] (An = U or Th; R = SiMe) with NaCCH and tetramethylethylenediamine (TMEDA) results in the formation of [An(C≡CH)(NR)] (, An = U; , An = Th), which can be isolated in good yields after workup. Similarly, the reaction of 3 equiv of NaCCH and TMEDA with [AnCl(NR)] results in the formation of [Na(TMEDA)][An(C≡CH)(NR)] (, An = U; , An = Th), which can be isolated in fair yields after workup. The reaction of with 2 equiv of KC and 1 equiv of 2.2.2-cryptand in tetrahydrofuran results in formation of the uranium(III) acetylide complex [K(2.2.2-cryptand)][U(C≡CH)(NR)] (). Thermolysis of or results in formation of the bimetallic dicarbide complexes [{An(NR)}(μ,η:η-C)] (, An = U; , An = Th), whereas the reaction of with [Th{(R)(SiMeH)}(NR)] results in the formation of [U(NR)(μ,η:η-C)Th(NR)] (). The C NMR chemical shifts of the α-acetylide carbon atoms in , , and exhibit a characteristic spin-orbit-induced downfield shift, due to participation of the 5f orbitals in the Th-C bonds. Magnetism measurements demonstrate that displays weak ferromagnetic coupling between the uranium(IV) centers ( = 1.78 cm).
[AnCl(NR)]（An = U或Th；R = SiMe）与NaCCH和四甲基乙二胺（TMEDA）反应生成[An(C≡CH)(NR)]（，An = U；，An = Th），后处理后可高收率分离得到。类似地，3当量的NaCCH和TMEDA与[AnCl(NR)]反应生成[Na(TMEDA)][An(C≡CH)(NR)]（，An = U；，An = Th），后处理后可中等收率分离得到。与2当量的KC和1当量的2.2.2-穴醚在四氢呋喃中反应生成铀（III）乙炔配合物[K(2.2.2-穴醚)][U(C≡CH)(NR)]（）。或的热解生成双金属二碳化物配合物[{An(NR)}(μ,η:η-C)]（，An = U；，An = Th），而与[Th{(R)(SiMeH)}(NR)]反应生成[U(NR)(μ,η:η-C)Th(NR)]（）。，和中α-乙炔碳原子的13C NMR化学位移由于5f轨道参与Th-C键而呈现出特征性的自旋轨道诱导的向低场位移。磁性测量表明显示出铀（IV）中心之间的弱铁磁耦合（J = 1.78 cm−1）。
