Aromatic Methoxylation and Hydroxylation by Organometallic High-Valent Nickel Complexes
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- 作者：Wen Zhou ; Jason W. Schultz ; Nigam P. Rath ; Liviu M. Mirica
- 刊名：Journal of the American Chemical Society
- 出版年：2015
- 出版时间：June 24, 2015
- 年：2015
- 卷：137
- 期：24
- 页码：7604-7607
- 全文大小：300K
- ISSN：1520-5126
文摘
Herein we report the synthesis and reactivity of several organometallic Nip>III p> complexes stabilized by a modified tetradentate pyridinophane ligand containing one phenyl group. A room temperature stable dicationic Nip>III p>鈥揹isolvento complex was also isolated, and the presence of two available cis coordination sites in this complex offers an opportunity to probe the C-heteroatom bond formation reactivity of high-valent Ni centers. Interestingly, the Nip>III p>-dihydroxide and Nip>III p>-dimethoxide species can be synthesized, and they undergo aryl methoxylation and hydroxylation that is favored by addition of oxidant, which also limits the 尾-hydride elimination side reaction. Overall, these results provide strong evidence for the involvement of high-valent organometallic Ni species, possibly both Nip>III p> and Nip>IV p> species, in oxidatively induced C-heteroatom bond formation reactions.