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?

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...

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Published inJournal of the American Chemical Society Vol. 134; no. 31; pp. 13035 - 13045
Main Authors Tran, Ba L., Pinter, Balazs, Nichols, Adam J., Konopka, Felicia T., Thompson, Rick, Chen, Chun-Hsing, Krzystek, J., Ozarowski, Andrew, Telser, Joshua, Baik, Mu-Hyun, Meyer, Karsten, Mindiola, Daniel J.
Format Journal Article
LanguageEnglish
Published WASHINGTON Amer Chemical Soc 08.08.2012
Subjects
Chemistry
Chemistry, Multidisciplinary
Physical Sciences
Science & Technology
TRANSITION-METAL DIMERS
MOLECULAR CALCULATIONS
ELECTRON-PARAMAGNETIC-RESONANCE
EFFECTIVE CORE POTENTIALS
REDUCTIVE CLEAVAGE
RAY CRYSTAL-STRUCTURES
DINITROGEN CLEAVAGE
TRIAMIDOAMINE LIGANDS
BETA-DIKETIMINATE LIGAND
DIAMIDOAMINE COMPLEX
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Summary: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).
ISSN:0002-7863
1520-5126
DOI:10.1021/ja303360v