Solution Synthesis, Structure, and CO2 Reduction Reactivity of a Scandium(II) Complex, {Sc[N(SiMe3)2]3}
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...
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Published in | Angewandte Chemie International Edition Vol. 56; no. 8; pp. 2050 - 2053 |
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Main Authors | , , , , , |
Format | Journal Article |
Language | English |
Published |
Weinheim
Wiley Subscription Services, Inc
13.02.2017
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Edition | International ed. in English |
Subjects | |
Online Access | Get full text |
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Summary: | 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.
Scandium's crowning: The first crystallographically characterizable complex of scandium in the +2 oxidation state was isolated from the reduction of Sc(NR2)3 (R=SiMe3). The low oxidation state was characterized by EPR and UV/Vis spectroscopy and DFT calculations. Reactivity studies with CO2 resulted in the isolation of both an oxalate complex and a rare CO2− species. |
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Bibliography: | ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
ISSN: | 1433-7851 1521-3773 |
DOI: | 10.1002/anie.201611758 |