A Planar Three-Coordinate Vanadium(II) Complex and the Study of Terminal Vanadium Nitrides from N2: A Kinetic or Thermodynamic Impediment to N–N Bond Cleavage?

A Planar Three-Coordinate Vanadium(II) Complex and the Study of Terminal Vanadium Nitrides from N2: 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 N2 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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Veröffentlicht in:Journal of the American Chemical Society 2012-08, Vol.134 (31), p.13035-13045
Hauptverfasser: 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: Artikel
Sprache:eng
Schlagworte:
Models, Molecular
Nitrogen - chemistry
Organometallic Compounds - chemistry
Spectrum Analysis, Raman
Thermodynamics
Vanadium - chemistry
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Zusammenfassung:We report the first mononuclear three-coordinate vanadium(II) complex [(nacnac)V(ODiiP)] and its activation of N2 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 N2 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[ t Bu]Ar)3], and the S = 1 system [(Ar[ t Bu]N)3Mo]2(μ2-η1:η1-N2).
ISSN:0002-7863
1520-5126
DOI:10.1021/ja303360v