Linear and Nonlinear Two-Coordinate Vanadium Complexes: Synthesis, Characterization, and Magnetic Properties of V(II) Amides
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- 作者：Jessica N. Boynton ; Jing-Dong Guo ; James C. Fettinger ; Christopher E. Melton ; Shigeru Nagase ; Philip P. Power
- 刊名：The Journal of the American Chemical Society
- 出版年：2013
- 出版时间：July 24, 2013
- 年：2013
- 卷：135
- 期：29
- 页码：10720-10728
- 全文大小：540K
- 年卷期：v.135,no.29(July 24, 2013)
- ISSN：1520-5126
文摘
The synthesis and characterization of the first stable two-coordinate vanadium complexes are described. The vanadium(II) primary amido derivative V{N(H)AriPr6}2 [AriPr6 = C6H3-2,6-(C6H2-2,4,6-iPr3)2] (1) was synthesized via the reaction of LiN(H)AriPr6 with the V(III) complex VCl3路2NMe3 or the V(II) salt [V2Cl3(THF)6]+I鈥?/sup> in a 2:1 and 4:1 stoichiometry, respectively. Reaction of the less crowded LiN(H)ArMe6 with [V2Cl3(THF)6]+I鈥?/sup> afforded V{N(H)ArMe6}2 [ArMe6 = C6H3-2,6-(C6H2-2,4,6-Me3)2] (2), which has a nonlinear [N鈥揤鈥揘 = 123.47(9)掳] vanadium coordination. Magnetometry studies showed that V{N(H)AriPr6}2 and V{N(H)ArMe6}2 have ambient temperature magnetic moments of 3.41 and 2.77 渭B, respectively, which are consistent with a high-spin d3 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 渭B. DFT calculations showed that the major absorptions in their UV鈥搗is 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)ArMe6}2]2(渭-O鈥揕i鈥揙)2 (3).