Electronic Structure of Nickel(II) and Zinc(II) Borohydrides from Spectroscopic Measurements and Computational Modeling

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• 作者：Patrick J. Desrochers ; Christopher A. Sutton ; Micah L. Abrams ; Shengfa Ye ; Frank Neese ; Joshua Telser ; Andrew Ozarowski ; J. Krzystek
• 刊名：Inorganic Chemistry
• 出版年：2012
• 出版时间：March 5, 2012
• 年：2012
• 卷：51
• 期：5
• 页码：2793-2805
• 全文大小：596K
• 年卷期：v.51,no.5(March 5, 2012)
• ISSN：1520-510X

文摘

The previously reported Ni(II) complex, Tp*Ni(魏³-BH₄) (Tp* = hydrotris(3,5-dimethylpyrazolyl)borate anion), which has an S = 1 spin ground state, was studied by high-frequency and -field electron paramagnetic resonance (HFEPR) spectroscopy as a solid powder at low temperature, by UV鈥搗is鈥揘IR spectroscopy in the solid state and in solution at room temperature, and by paramagnetic ¹¹B NMR. HFEPR provided its spin Hamiltonian parameters: D = 1.91(1) cm^鈥?, E = 0.285(8) cm^鈥?, g = [2.170(4), 2.161(3), 2.133(3)]. Similar, but not identical parameters were obtained for its borodeuteride analogue. The previously unreported complex, Tp*Zn(魏²-BH₄), was prepared, and IR and NMR spectroscopy allowed its comparison with analogous closed shell borohydride complexes. Ligand-field theory was used to model the electronic transitions in the Ni(II) complex successfully, although it was less successful at reproducing the zero-field splitting (zfs) parameters. Advanced computational methods, both density functional theory (DFT) and ab initio wave function based approaches, were applied to these Tp*MBH₄ complexes to better understand the interaction between these metals and borohydride ion. DFT successfully reproduced bonding geometries and vibrational behavior of the complexes, although it was less successful for the spin Hamiltonian parameters of the open shell Ni(II) complex. These were instead best described using ab initio methods. The origin of the zfs in Tp*Ni(魏³-BH₄) is described and shows that the relatively small magnitude of D results from several spin鈥搊rbit coupling (SOC) interactions of large magnitude, but with opposite sign. Spin鈥搒pin coupling (SSC) is also shown to be significant, a point that is not always appreciated in transition metal complexes. Overall, a picture of bonding and electronic structure in open and closed shell late transition metal borohydrides is provided, which has implications for the use of these complexes in catalysis and hydrogen storage.