Unexpected Formation of Chiral Pincer CNN Nickel Complexes with 尾-Diketiminato Type Ligands via C鈥揌 Activation: Synthesis, Properties, Structures, and Computational Studies

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• 作者：Zhengliang Lu ; Srinivas Abbina ; Jared R. Sabin ; Victor N. Nemykin ; Guodong Du
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：February 4, 2013
• 年：2013
• 卷：52
• 期：3
• 页码：1454-1465
• 全文大小：712K
• 年卷期：v.52,no.3(February 4, 2013)
• ISSN：1520-510X

文摘

Reaction of lithiated chiral, unsymmetric 尾-diketimine type ligands HL^2a鈥?b>e containing oxazoline moiety (HL^2a鈥?b>e = 2-(2鈥?R₁NH)-phenyl-4-R₂-oxazoline) with trans-NiCl(Ph)(PPh₃)₂ afforded a series of new chiral CNN pincer type nickel complexes (3a鈥?b>3e) via an unexpected cyclometalation at benzylic or aryl C鈥揌 positions. Single crystal X-ray diffraction analysis established the pincer coordination mode and the strained conformation. Chirality, and in one case, racemization of the target nickel complexes were confirmed by circular dichroism (CD) spectroscopy. Electronic structure and band assignments in experimental UV鈥搗is and CD spectra were discussed on the basis of Density Functional Theory (DFT) and time-dependent (TD) DFT calculations.