Solution Synthesis, Structure, and CO₂ Reduction Reactivity of a Scandium(II) Complex, {Sc[N(SiMe₃)₂]₃}⁻

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• 作者：David H. Woen ; Guo P. Chen ; Dr. Joseph W. Ziller ; Dr. Timothy J. Boyle ; Prof. Dr. Filipp Furche and Prof. Dr. William J. Evans
• 刊名：Angewandte Chemie International Edition
• 出版年：2017
• 出版时间：February 13, 2017
• 年：2017
• 卷：56
• 期：8
• 页码：2050-2053
• 全文大小：853K
• ISSN：1521-3773

文摘

The first crystallographically characterizable complex of Sc²⁺, [Sc(NR₂)₃]⁻ (R=SiMe₃), has been obtained by LnA₃/M reactions (Ln=rare earth metal; A=anionic ligand; M=alkali metal) involving reduction of Sc(NR₂)₃ with K in the presence of 2.2.2-cryptand (crypt) and 18-crown-6 (18-c-6) and with Cs in the presence of crypt. Dark maroon [K(crypt)]⁺, [K(18-c-6)]⁺, and [Cs(crypt)]⁺ salts of the [Sc(NR₂)₃]⁻ anion are formed, respectively. The formation of this oxidation state of Sc is also indicated by the eight-line EPR spectra arising from the I=7/2 ⁴⁵Sc nucleus. The Sc(NR₂)₃ reduction differs from Ln(NR₂)₃ reactions (Ln=Y and lanthanides) in that it occurs under N₂ without formation of isolable reduced dinitrogen species. [K(18-c-6)][Sc(NR₂)₃] reacts with CO₂ to produce an oxalate complex, {K₂(18-c-6)₃}{[(R₂N)₃Sc]₂(μ-C₂O₄-κ¹O:κ¹O′′)}, and a CO₂⁻ radical anion complex, [(R₂N)₃Sc(μ-OCO-κ¹O:κ¹O′)K(18-c-6)]_n.