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 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-η(1):η(1)-N2).
Department of Chemistry and Molecular Structure Center, Indiana University , Bloomington, Indiana 47405, United States.
Ba L
BL
Tran
Balazs
B
Pinter
Adam J
AJ
Nichols
Felicia T
FT
Konopka
Rick
R
Thompson
Chun-Hsing
CH
Chen
J
J
Krzystek
Andrew
A
Ozarowski
Joshua
J
Telser
Mu-Hyun
MH
Baik
Karsten
K
Meyer
Daniel J
DJ
Mindiola
D008958:Models, Molecular; D009584:Nitrogen / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D013059:Spectrum Analysis, Raman; D013816:Thermodynamics; D014639:Vanadium / Q000737:chemistry*
D009942:Organometallic Compounds; D014639:Vanadium; D009584:Nitrogen