Quantifying the Electron Donor and Acceptor Abilities of the Ketimide Ligands in M(N鈺怌tBu2)4 (M = V, Nb, Ta)

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• 作者：Peter L. Damon ; Cameron J. Liss ; Richard A. Lewis ; Simona Morochnik ; David E. Szpunar ; Joshua Telser ; Trevor W. Hayton
• 刊名：Inorganic Chemistry
• 出版年：2015
• 出版时间：October 19, 2015
• 年：2015
• 卷：54
• 期：20
• 页码：10081-10095
• 全文大小：755K
• ISSN：1520-510X

文摘

Addition of 4 equiv of Li(N鈺怌tBu2) to VCl3 in THF, followed by addition of 0.5 equiv of I2, generates the homoleptic V(IV) ketimide complex, V(N鈺怌tBu2)4 (1), in 42% yield. Similarly, reaction of 4 equiv of Li(N鈺怌tBu2) with NbCl4(THF)2 in THF affords the homoleptic Nb(IV) ketimide complex, Nb(N鈺怌tBu2)4 (2), in 55% yield. Seeking to extend the series to the tantalum congener, a new Ta(IV) starting material, TaCl4(TMEDA) (3), was prepared via reduction of TaCl5 with Et3SiH, followed by addition of TMEDA. Reaction of 3 with 4 equiv of Li(N鈺怌tBu2) in THF results in the isolation of a Ta(V) ketimide complex, Ta(Cl)(N鈺怌tBu2)4 (5), which can be isolated in 32% yield. Reaction of 5 with Tl(OTf) yields Ta(OTf)(N鈺怌tBu2)4 (6) in 44% yield. Subsequent reduction of 6 with Cp*2Co in toluene generates the homoleptic Ta(IV) congener Ta(N鈺怌tBu2)4 (7), although the yields are poor. All three homoleptic group 5 ketimide complexes exhibit squashed tetrahedral geometries in the solid state, as determined by X-ray crystallography. This geometry leads to a dx2鈥?i>y21 (2B1 in D2d) ground state, as supported by DFT calculations. EPR spectroscopic analysis of 1 and 2, performed at X- and Q-band frequencies (鈭? and 35 GHz, respectively), further supports the 2B1 ground-state assignment, whereas comparison of 1, 2, and 7 with related group 5 tetra(aryl), tetra(amido), and tetra(alkoxo) complexes shows a higher M鈥揕 covalency in the ketimide鈥搈etal interaction. In addition, a ligand field analysis of 1 and 2 demonstrates that the ketimide ligand is both a strong 蟺-donor and strong 蟺-acceptor, an unusual combination found in very few organometallic ligands.