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Updated: May 10, 2026
Chemical Vapor Deposition of an Organic Magnet, Vanadium Tetracyanoethylene
Published on: July 3, 2015
Linear and nonlinear two-coordinate vanadium complexes: synthesis, characterization, and magnetic properties of V(II)
Jessica N Boynton1, Jing-Dong Guo, James C Fettinger
1Department of Chemistry, University of California-Davis, 1 Shields Avenue, Davis, California 95616, USA.
Abstract:
The synthesis and characterization of the first stable two-coordinate vanadium complexes are described. The vanadium(II) primary amido derivative V{N(H)Ar(iPr6)}2 [Ar(iPr6) = C6H3-2,6-(C6H2-2,4,6-iPr3)2] (1) was synthesized via the reaction of LiN(H)Ar(iPr6) with the V(III) complex VCl3·2NMe3 or the V(II) salt [V2Cl3(THF)6](+)I(-) in a 2:1 and 4:1 stoichiometry, respectively. Reaction of the less crowded LiN(H)Ar(Me6) with [V2Cl3(THF)6](+)I(-) afforded V{N(H)Ar(Me6)}2 [Ar(Me6) = C6H3-2,6-(C6H2-2,4,6-Me3)2] (2), which has a nonlinear [N-V-N = 123.47(9)°] vanadium coordination. Magnetometry studies showed that V{N(H)Ar(iPr6)}2 and V{N(H)Ar(Me6)}2 have ambient temperature magnetic moments of 3.41 and 2.77 μB, respectively, which are consistent with a high-spin d(3) electron configuration. These values suggest a significant spin orbital angular momentum contribution that leads to a magnetic moment that is lower than their spin-only value of 3.87 μB. DFT calculations showed that the major absorptions in their UV-vis spectra were due to ligand to metal charge transfer transitions. Exposure of the reaction mixture for 2 to dry O2 resulted in the formation of the diamagnetic V(V) oxocluster [V{N(H)Ar(Me6)}2]2(μ-O-Li-O)2 (3).
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