Chen Runhai, Qin Guorui, Li Shihui, Edwards Alison J, Piltz Ross O, Del Rosal Iker, Maron Laurent, Cui Dongmei, Cheng Jianhua
State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, No. 5625, Renmin Street, Changchun, 130022, China.
Australian Centre for Neutron Scattering, Australian Nuclear Science and Technology Organization, New IIIawarra Road, Lucas Heights, NSW, 2234, Australia.
Angew Chem Int Ed Engl. 2020 Jul 6;59(28):11250-11255. doi: 10.1002/anie.202002303. Epub 2020 May 7.
Hydrogenolysis of alkyl-substituted cyclopentadienyl (Cp ) ligated thorium tribenzyl complexes [(Cp )Th(p-CH -C H -Me) ] (1-6) afforded the first examples of molecular thorium trihydrido complexes [(Cp )Th(μ-H) ] (Cp =C H ( Bu) or C H (SiMe ) , n=5; C Me SiMe , n=6; C Me , n=7; C Me H, n=8; 7-10 and 12) and [(Cp ) Th H ] (Cp =C H SiMe ; 13). The nuclearity of the metal hydride clusters depends on the steric profile of the cyclopentadienyl ligands. The hydrogenolysis intermediate, tetra-nuclear octahydrido thorium dibenzylidene complex [(Cp )Th(μ-H) ] (μ-p-CH-C H -Me) (Cp =C H ( Bu) ) (11) was also isolated. All of the complexes were characterized by NMR spectroscopy and single-crystal X-ray analysis. Hydride positions in [(Cp )Th(μ-H) ] (Cp =C Me H) were further precisely confirmed by single-crystal neutron diffraction. DFT calculations strengthen the experimental assignment of the hydride positions in the complexes 7 to 12.
烷基取代的环戊二烯基（Cp）配位的三苄基钍配合物[(Cp)Th(p-CH₂-C₆H₄-Me)₃]（1 - 6）的氢解反应得到了首例分子型三氢化钍配合物[(Cp)Th(μ-H)₃]（Cp = C₅H₄(t-Bu)或C₅H₄(SiMe₃)，n = 5；C₅Me₄SiMe₃，n = 6；C₅Me₅，n = 7；C₅Me₄H，n = 8；7 - 10和12）以及[(Cp*)ThH₃]（Cp* = C₅H₄SiMe₃；13）。金属氢化物簇的核数取决于环戊二烯基配体的空间构型。氢解反应中间体，四核八氢化钍二亚苄基配合物(Cp)Th(μ-H)₃（Cp = C₅H₄(t-Bu)）（11）也被分离出来。所有配合物均通过核磁共振光谱和单晶X射线分析进行了表征。[(Cp)Th(μ-H)₃]（Cp = C₅Me₄H）中氢化物的位置通过单晶中子衍射进一步精确确认。密度泛函理论计算强化了配合物7至12中氢化物位置的实验归属。
