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End-On Bridging Dinitrogen Complex of Scandium

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.7b08456· OSTI ID:1473943
 [1];  [1];  [1];  [2];  [1];  [1]
  1. Univ. of California, Irvine, CA (United States)
  2. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
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The first (N=N)2- complex of a rare-earth metal with an end-on dinitrogen bridge, {K(crypt)}2{[(R2N)3Sc]2[μ-η1:η1-n2]} (crypt = 2.2.2-cryptand, R = SiMe3), has been isolated from the reduction of Sc(NR2)3 under dinitrogen at —35 °C and characterized by X-ray crystallography. The structure differs from the characteristic side-on structures previously observed for over 40 crystallographically-characterized rare-earth metal (N=N)2- complexes of formula [A2Ln(THF)x]2[μ-η2:η2-N2] (Ln = Sc, Y, and lanthanides; x = 0, 1; A = anionic ligand such as amide, cyclopentadienide, and aryloxide). The 1.221(3) Å N—N distance and the 1644 cm-1 Raman stretch are consistent with the presence of an (N=N)2- bridge. The observed paramagnetism of the complex by NMR spectroscopy and Evans method measurements is consistent with DFT calculations that suggest a triplet( 3A2) ground state in D3 symmetry involving two degenerate Sc—N2—Sc bonding orbitals. Upon brief exposure of the orange Sc3+ bridging dinitrogen complex to UV-light, photolysis to form the monomeric Sc2+ complex, [K(crypt)][Sc(NR2)3], was observed. Conversion of the Sc2+ complex to the SO3+ dinitrogen complex was not observed with this crypt system, but it did occur with the 18-crown-6 (crown) analog which formed {K(crown)}2{[(R2N)3Sc]2[μ-η1:η1-N2]}. This suggests the importance of the alkali metal chelating agent in the reversibility of dinitrogen binding in this scandium system.
Research Organization:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Organization:
USDOE National Nuclear Security Administration (NNSA)
Grant/Contract Number:
AC04-94AL85000
OSTI ID:
1473943
Report Number(s):
SAND--2018-10055J; 667860
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 42 Vol. 139; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

References (47)

?-Bonded Nitrogen in a Crystalline Nickel-Lithium Complex journal December 1973
Molecular Structure of a π-Dinitrogen-Nickel-Lithium Complex journal December 1973
Lanthanum Does Form Stable Molecular Compounds in the +2 Oxidation State journal February 2008
Catalytic Reduction of Dinitrogen to Ammonia by Molybdenum: Theory versus Experiment journal June 2008
Dinitrogen Reduction and CH Activation by the Divalent Organoneodymium Complex [(C 5 H 2 t Bu 3 ) 2 Nd(μ-I)K([18]crown-6)] journal January 2009
A Dimetalloxycarbene Bonding Mode and Reductive Coupling Mechanism for Oxalate Formation from CO 2 journal June 2015
Solution Synthesis, Structure, and CO 2 Reduction Reactivity of a Scandium(II) Complex, {Sc[N(SiMe 3 ) 2 ] 3 } − journal January 2017
Iron–dinitrogen coordination chemistry: Dinitrogen activation and reactivity journal September 2010
Developing more sustainable processes for ammonia synthesis journal September 2013
Dinitrogen activation by group 4 and group 5 metal complexes supported by phosphine-amido containing ligand manifolds journal March 2017
Dinitrogen Binding and Cleavage by Multinuclear Iron Complexes journal June 2015
Tutorial on the Role of Cyclopentadienyl Ligands in the Discovery of Molecular Complexes of the Rare-Earth and Actinide Metals in New Oxidation States journal September 2016
Side-on End-on Bound Dinitrogen: An Activated Bonding Mode That Facilitates Functionalizing Molecular Nitrogen journal September 2008
Dinitrogen Coordination Chemistry:  On the Biomimetic Borderlands journal February 2004
Recent advances in the chemistry of nitrogen fixation journal December 1978
Isolation and x-ray crystal structure of the first dinitrogen complex of an f-element metal, [(C5Me5)2Sm]2N2 journal September 1988
"Side-on" dinitrogen-transition metal complexes. The molecular structure of {C6H5[Na.O(C2H5)2]2[(C6H5)2Ni]2N2NaLi6(OC2H5)4.O(C2H5)2}2 journal January 1976
Preparation of a dinitrogen complex of bis(pentamethylcyclopentadienyl)zirconium(II). Isolation and protonation leading to stoichiometric reduction of dinitrogen to hydrazine journal September 1974
Reversible Binding and Reduction of Dinitrogen by a Uranium(III) Pentalene Complex journal August 2002
Reduction of Dinitrogen to Planar Bimetallic M 2 (μ - η 2 : η 2 -N 2 ) Complexes of Y, Ho, Tm, and Lu Using the K/Ln[N(SiMe 3 ) 2 ] 3 Reduction System journal January 2004
Expanding Dinitrogen Reduction Chemistry to Trivalent Lanthanides via the LnZ 3 /Alkali Metal Reduction System:  Evaluation of the Generality of Forming Ln 2 (μ - η 2 : η 2 -N 2 ) Complexes via LnZ 3 /K journal November 2004
Studies of Low-Coordinate Iron Dinitrogen Complexes journal January 2006
Heteroleptic Tm(II) Complexes:  One More Success for Trofimenko's Scorpionates journal February 2008
Synthesis, Structure, and Density Functional Theory Analysis of a Scandium Dinitrogen Complex, [(C 5 Me 4 H) 2 Sc] 2 (μ-η 2 :η 2 -N 2 ) journal August 2010
Synthesis of the (N 2 ) 3− Radical from Y 2+ and Its Protonolysis Reactivity To Form (N 2 H 2 ) 2− via the Y[N(SiMe 3 ) 2 ] 3 /KC 8 Reduction System journal March 2011
Synthesis of a Crystalline Molecular Complex of Y 2+ , [(18-crown-6)K][(C 5 H 4 SiMe 3 ) 3 Y] journal October 2011
Isolation of (CO) 1– and (CO 2 ) 1– Radical Complexes of Rare Earths via Ln(NR 2 ) 3 /K Reduction and [K 2 (18-crown-6) 2 ] 2+ Oligomerization journal March 2012
Expanding Rare-Earth Oxidation State Chemistry to Molecular Complexes of Holmium(II) and Erbium(II) journal May 2012
Completing the Series of +2 Ions for the Lanthanide Elements: Synthesis of Molecular Complexes of Pr 2+ , Gd 2+ , Tb 2+ , and Lu 2+ journal May 2013
Fine-Tuning the Energy Barrier for Metal-Mediated Dinitrogen N≡N Bond Cleavage journal July 2014
Shining Light on Dinitrogen Cleavage: Structural Features, Redox Chemistry, and Photochemistry of the Key Intermediate Bridging Dinitrogen Complex journal June 2008
Complex of Dinitrogen with Trivalent Uranium journal January 1998
Dinitrogen Labile Coordination versus Four-Electron Reduction, THF Cleavage, and Fragmentation Promoted by a (calix-tetrapyrrole)Sm(II) Complex journal November 2000
Bis(cyclopentadienyl) Titanium Dinitrogen Chemistry:  Synthesis and Characterization of a Side-on Bound Haptomer journal April 2007
Side-on Dinitrogen Complexes of Titanocenes with Disubstituted Cyclopentadienyl Ligands: Synthesis, Structure, and Spectroscopic Characterization journal April 2012
Thermally Stable Uranium Dinitrogen Complex with Siloxide Supporting Ligands journal July 2013
Bis(tetramethylcyclopentadienyl)titanium Chemistry. Molecular Structures of [(C 5 HMe 4 )(μ-η 1 :η 5 -C 5 Me 4 )Ti] 2 and [(C 5 HMe 4 ) 2 Ti] 2 N 2 journal January 1996
Examining the relationship between coordination mode and reactivity of dinitrogen journal March 2017
Dinitrogen functionalization with bis(cyclopentadienyl) complexes of zirconium and hafnium journal January 2007
Raman spectroscopy of the N–N bond in rare earth dinitrogen complexes journal January 2016
The fixation and reduction of dinitrogen using lanthanides: praseodymium and neodymium meso-octaethylporphyrinogen–dinitrogen complexes journal January 1998
Theoretical investigation of the pathway for reductive cleavage of dinitrogen by a vanadium diamidoamine complex journal January 2000
Metal–dioxygen and metal–dinitrogen complexes: where are the electrons? journal January 2010
Organometallic compounds of bivalent europium, ytterbium, and samarium journal January 1971
400. The determination of the paramagnetic susceptibility of substances in solution by nuclear magnetic resonance journal January 1959
The importance of cyclopentadienyl substituent effects in group 4 metallocene dinitrogen chemistry journal April 2005
Early developments in lanthanide-based dinitrogen reduction chemistry journal April 2005

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Single Electron Transfer to Diazomethane–Borane Adducts Prompts C−H Bond Activations journal October 2019
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Isolation of reactive Ln( ii ) complexes with C 5 H 4 Me ligands (Cp Me ) using inverse sandwich countercations: synthesis and structure of [(18-crown-6)K(μ-Cp Me )K(18-crown-6)][Cp Me 3 Ln II ] (Ln = Tb, Ho) journal January 2018
Addition reactions and diazomethane capture by the intramolecular P–O–B FLP: t Bu 2 POBcat journal January 2020

Figures / Tables (4)

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Scheme 1(p. 3)figure Scheme 1

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