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Solution Synthesis, Structure, and CO 2 Reduction Reactivity of a Scandium(II) Complex, {Sc[N(SiMe 3 ) 2 ] 3 } −
Author(s) -
Woen David H.,
Chen Guo P.,
Ziller Joseph W.,
Boyle Timothy J.,
Furche Filipp,
Evans William J.
Publication year - 2017
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201611758
Subject(s) - chemistry , scandium , oxalate , crystallography , electron paramagnetic resonance , metal , alkali metal , reactivity (psychology) , ligand (biochemistry) , oxidation state , stereochemistry , ion , medicinal chemistry , inorganic chemistry , nuclear magnetic resonance , medicine , biochemistry , physics , alternative medicine , receptor , organic chemistry , pathology
The first crystallographically characterizable complex of Sc 2+ , [Sc(NR 2 ) 3 ] − (R=SiMe 3 ), has been obtained by LnA 3 /M reactions (Ln=rare earth metal; A=anionic ligand; M=alkali metal) involving reduction of Sc(NR 2 ) 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(NR 2 ) 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 45 Sc nucleus. The Sc(NR 2 ) 3 reduction differs from Ln(NR 2 ) 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(NR 2 ) 3 ] reacts with CO 2 to produce an oxalate complex, {K 2 (18‐c‐6) 3 }{[(R 2 N) 3 Sc] 2 (μ‐C 2 O 4 ‐ κ 1 O: κ 1 O′′)}, and a CO 2 − radical anion complex, [(R 2 N) 3 Sc(μ‐OCO‐ κ 1 O: κ 1 O′)K(18‐c‐6)] n .
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