A Planar Three-Coordinate Vanadium(II) Complex and the Study of Terminal Vanadium Nitrides from N-2: A Kinetic or Thermodynamic Impediment to N-N Bond Cleavage?

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We report the first mononuclear three-coordinate vanadium(II) complex [(nacnac)V(ODiiP)] and its activation of N-2 to form an end-on bridging dinitrogen complex with a topologically linear V(III)N2V(III) core and where each vanadium center antiferromagnetically couples to give a ground state singlet with an accessible triplet state as inferred by HFEPR spectroscopy. In addition to investigating the conversion of N-2 to the terminal nitride (as well as the microscopic reverse process), we discuss its similarities and contrasts to the isovalent d(3) system, [Mo(N[Bu-t]Ar)(3)], and the S = 1 system [(Ar[Bu-t]N)(3)Mo](2)(mu(2)-eta(1):eta(1)-N-2).
Publisher
AMER CHEMICAL SOC
Issue Date
2012-08
Language
English
Article Type
Article
Keywords

ELECTRON-PARAMAGNETIC-RESONANCE; EFFECTIVE CORE POTENTIALS; BETA-DIKETIMINATE LIGAND; TRANSITION-METAL DIMERS; RAY CRYSTAL-STRUCTURES; DINITROGEN CLEAVAGE; MOLECULAR CALCULATIONS; REDUCTIVE CLEAVAGE; TRIAMIDOAMINE LIGANDS; DIAMIDOAMINE COMPLEX

Citation

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.134, no.31, pp.13035 - 13045

ISSN
0002-7863
DOI
10.1021/ja303360v
URI
http://hdl.handle.net/10203/203302
Appears in Collection
CH-Journal Papers(저널논문)
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