期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 61, 期 50, 页码 -出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202211627
关键词
Actinides; Arsinidene; Density Functional Theory; Multiple Bonds; Phosphinidene
资金
- UK Engineering and Physical Sciences Research Council [EP/M027015/1, EP/P001386/1, EP/S033181/1, EP/T011289/1]
- European Research Council [CoG612724]
- Deutsche Forschungsgemeinschaft [SL104/10-1]
- Alexander von Humboldt Foundation
- University of Manchester
The study reports the direct synthesis of terminal pnictidenes and their conversion to pnictides, highlighting the importance of the super-bulky Tren(TCHS) ligand. The findings provide valuable insights into thorium-arsenic bonding.
We report the direct synthesis of the terminal pnictidenes [An(Tren(TCHS))(PnH)][M(2,2,2-cryptand)] (Tren(TCHS)={N(CH2CH2NSiCy3)(3)}(3-); An/Pn/M=Th/P/Na 5, Th/As/K 6, U/P/Na 7, U/As/K 8) and their conversion to the pnictides [An(Tren(TCHS))(PnH(2))] (An/Pn=Th/P 9, Th/As 10, U/P 11, U/As 12). Use of the super-bulky Tren(TCHS) ligand was essential to accessing complete families, and 6 is an unprecedented example of a terminal thorium-arsinidene complex and only the second structurally authenticated parent terminal arsinidene complex of any metal. Comparison of the terminal Th=AsH unit of 6 to the bridging ThAs(H)K linkage in structurally analogous [Th(Tren(TIPS)){mu-As(H)K(15-crown-5)}] (Tren(TIPS)={N(CH2CH2NSiPr3i)(3)}(3-)) reveals a stronger Th-As bond in the former compared to the latter, and a large response overall to the nature of the Th=AsH bonding upon removal of the electrostatically-bound K-ion; the sigma-bond changes little but the pi-bond is significantly perturbed.
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