The reaction of [AnCl(NR2)3] (An = U or Th; R = SiMe3) with NaCCH and tetramethylethylenediamine (TMEDA) results in the formation of [An(C≡CH)(NR2)3] (1, An = U; 2, An = Th), which can be isolated in good yields after workup. Similarly, the reaction of 3 equiv of NaCCH and TMEDA with [AnCl(NR2)3] results in the formation of [Na(TMEDA)][An(C≡CH)2(NR2)3] (4, An = U; 5, An = Th), which can be isolated in fair yields after workup. The reaction of 1 with 2 equiv of KC8 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)(NR2)3] (3). Thermolysis of 1 or 2 results in formation of the bimetallic dicarbide complexes [{An(NR2)3}2(μ,η1:η1-C2)] (6, An = U; 7, An = Th), whereas the reaction of 1 with [Th{N(R)(SiMe2CH2)}(NR2)2] results in the formation of [U(NR2)3(μ,η1:η1-C2)Th(NR2)3] (8). The 13C NMR chemical shifts of the α-acetylide carbon atoms in 2, 5, and 7 exhibit a characteristic spin–orbit-induced downfield shift, due to participation of the 5f orbitals in the Th–C bonds. Furthermore, magnetism measurements demonstrate that 6 displays weak ferromagnetic coupling between the uranium(IV) centers (J = 1.78 cm–1).
Kent, Greggory T., et al. "Synthesis of Parent Acetylide and Dicarbide Complexes of Thorium and Uranium and an Examination of Their Electronic Structures." Inorganic Chemistry, vol. 60, no. 20, Sep. 2021. https://doi.org/10.1021/acs.inorgchem.1c02064
Kent, Greggory T., Yu, Xiaojuan, Pauly, Christophe, Wu, Guang, Autschbach, Jochen, & Hayton, Trevor W. (2021). Synthesis of Parent Acetylide and Dicarbide Complexes of Thorium and Uranium and an Examination of Their Electronic Structures. Inorganic Chemistry, 60(20). https://doi.org/10.1021/acs.inorgchem.1c02064
Kent, Greggory T., Yu, Xiaojuan, Pauly, Christophe, et al., "Synthesis of Parent Acetylide and Dicarbide Complexes of Thorium and Uranium and an Examination of Their Electronic Structures," Inorganic Chemistry 60, no. 20 (2021), https://doi.org/10.1021/acs.inorgchem.1c02064
@article{osti_2479718,
author = {Kent, Greggory T. and Yu, Xiaojuan and Pauly, Christophe and Wu, Guang and Autschbach, Jochen and Hayton, Trevor W.},
title = {Synthesis of Parent Acetylide and Dicarbide Complexes of Thorium and Uranium and an Examination of Their Electronic Structures},
annote = {The reaction of [AnCl(NR2)3] (An = U or Th; R = SiMe3) with NaCCH and tetramethylethylenediamine (TMEDA) results in the formation of [An(C≡CH)(NR2)3] (1, An = U; 2, An = Th), which can be isolated in good yields after workup. Similarly, the reaction of 3 equiv of NaCCH and TMEDA with [AnCl(NR2)3] results in the formation of [Na(TMEDA)][An(C≡CH)2(NR2)3] (4, An = U; 5, An = Th), which can be isolated in fair yields after workup. The reaction of 1 with 2 equiv of KC8 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)(NR2)3] (3). Thermolysis of 1 or 2 results in formation of the bimetallic dicarbide complexes [{An(NR2)3}2(μ,η1:η1-C2)] (6, An = U; 7, An = Th), whereas the reaction of 1 with [Th{N(R)(SiMe2CH2)}(NR2)2] results in the formation of [U(NR2)3(μ,η1:η1-C2)Th(NR2)3] (8). The 13C NMR chemical shifts of the α-acetylide carbon atoms in 2, 5, and 7 exhibit a characteristic spin–orbit-induced downfield shift, due to participation of the 5f orbitals in the Th–C bonds. Furthermore, magnetism measurements demonstrate that 6 displays weak ferromagnetic coupling between the uranium(IV) centers (J = 1.78 cm–1).},
doi = {10.1021/acs.inorgchem.1c02064},
url = {https://www.osti.gov/biblio/2479718},
journal = {Inorganic Chemistry},
issn = {ISSN 0020-1669},
number = {20},
volume = {60},
place = {United States},
publisher = {American Chemical Society (ACS)},
year = {2021},
month = {09}}