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

被引：79
|
作者：
Woen, David H. [1 ]
Chen, Guo P. [1 ]
Ziller, Joseph W. [1 ]
Boyle, Timothy J. [2 ]
Furche, Filipp [1 ]
Evans, William J. [1 ]
机构：
[1] Univ Calif Irvine, Dept Chem, 1102 Nat Sci II, Irvine, CA 92697 USA
[2] Sandia Natl Labs, Adv Mat Lab, 1001 Univ Blvd SE, Albuquerque, NM 87106 USA
来源：
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2017年 / 56卷 / 08期
基金：
美国国家科学基金会;
关键词：
carbon dioxide; low-valent metals; rare earths; reduction; scandium; THE+2 OXIDATION-STATE; SIGMA-BOND METATHESIS; X-RAY-STRUCTURE; MOLECULAR-COMPLEXES; RARE-EARTH; DINITROGEN; CHEMISTRY; LIGAND; CRYSTAL; URANIUM;
D O I：
10.1002/anie.201611758
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
The first crystallographically characterizable complex of Sc2+, [Sc(NR2)(3)] (R=SiMe3), has been obtained by LnA(3)/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 Sc-45 nucleus. The Sc(NR2)(3) reduction differs from Ln(NR2)(3) reactions (Ln=Y and lanthanides) in that it occurs under N-2 without formation of isolable reduced dinitrogen species. [K(18-c-6)][Sc(NR2) 3] reacts with CO2 to produce an oxalate complex, {K-2(18-c-6)(3)}{[(R2N)(3)Sc](2)(mu-C2O4-kappa O-1:kappa O-1(''))}, and a CO2- radical anion complex, [(R2N)(3)Sc(mu-OCO-kappa O-1:kappa O-1')K(18-c-6)](n).
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收藏
页码：2050 / 2053
页数：4
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