title: Solution Synthesis, Structure, and CO2Reduction Reactivity of a Scandium(II) Complex, {Sc[N(SiMe3)2]3}<sup/>.
abstract: 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)3with 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=7/245Sc nucleus. The Sc(NR2)3reduction differs from Ln(NR2)3reactions (Ln=Y and lanthanides) in that it occurs under N2without formation of isolable reduced dinitrogen species. [K(18-c-6)][Sc(NR2)3] reacts with CO2to 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.
authors.affiliation: Department of Chemistry, University of California, Irvine, 1102 Natural Sciences II, Irvine, CA, 92697-2025, USA.
authors.forename: David H
authors.identifier: 0000-0002-5764-1453
authors.initials: DH
authors.lastname: Woen
authors.affiliation: Department of Chemistry, University of California, Irvine, 1102 Natural Sciences II, Irvine, CA, 92697-2025, USA.
authors.forename: Guo P
authors.identifier: 0000-0002-4743-4450
authors.initials: GP
authors.lastname: Chen
authors.affiliation: Department of Chemistry, University of California, Irvine, 1102 Natural Sciences II, Irvine, CA, 92697-2025, USA.
authors.forename: Joseph W
authors.identifier: 0000-0001-7404-950X
authors.initials: JW
authors.lastname: Ziller
authors.affiliation: Sandia National Laboratories, Advanced Materials Laboratory, 1001 University Blvd. SE, Albuquerque, NM, 87106, USA.
authors.forename: Timothy J
authors.identifier: 0000-0002-1251-5592
authors.initials: TJ
authors.lastname: Boyle
authors.affiliation: Department of Chemistry, University of California, Irvine, 1102 Natural Sciences II, Irvine, CA, 92697-2025, USA.
authors.forename: Filipp
authors.identifier: 0000-0001-8520-3971
authors.initials: F
authors.lastname: Furche
authors.affiliation: Department of Chemistry, University of California, Irvine, 1102 Natural Sciences II, Irvine, CA, 92697-2025, USA.
authors.forename: William J
authors.identifier: 0000-0002-0651-418X
authors.initials: WJ
authors.lastname: Evans
keywords: carbon dioxide; low-valent metals; rare earths; reduction; scandium