Carbon鈥揌ydrogen Bond Activation, C鈥揘 Bond Coupling, and Cycloaddition Reactivity of a Three-Coordinate Nickel Complex Featuring a Terminal Imido Ligand

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• 作者：Daniel J. Mindiola ; Rory Waterman ; Vlad M. Iluc ; Thomas R. Cundari ; Gregory L. Hillhouse
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：December 15, 2014
• 年：2014
• 卷：53
• 期：24
• 页码：13227-13238
• 全文大小：628K
• ISSN：1520-510X

文摘

The three-coordinate imidos (dtbpe)Ni鈺怤R (dtbpe = ^tBu₂PCH₂CH₂P^tBu_2, R = 2,6-ⁱPr₂C₆H₃, 2,4,6-Me₃C₆H₂ (Mes), and 1-adamantyl (Ad)), which contain a legitimate Ni鈥揘 double bond as well as basic imido nitrogen based on theoretical analysis, readily deprotonate HC鈮Ph to form the amide acetylide species (dtbpe)Ni{NH(Ar)}(C鈮Ph). In the case of R = 2,6-ⁱPr₂C₆H₃, reductive carbonylation results in formation of the (dtbpe)Ni(CO)₂ along with the N鈥揅 coupled product keteneimine PhCH鈺怌鈺怤(2,6- ⁱPr₂C₆H₃). Given the ability of the Ni鈺怤 bond to have biradical character as suggested by theoretical analysis, H atom abstraction can also occur in (dtbpe)Ni鈺怤{2,6-ⁱPr₂C₆H₃} when this species is treated with HSn(ⁿBu)₃. Likewise, the microscopic reverse reaction鈥攃onversion of the Ni(I) anilide (dtbpe)Ni{NH(2,6-ⁱPr₂C₆H₃)} to the imido (dtbpe)Ni鈺怤{2,6-ⁱPr₂C₆H₃}鈥攊s promoted when using the radical Mes*O^{鈥?/sup> (Mes* = 2,4,6-tBu₃C₆H₂). Reactivity studies involving the imido complexes, in particular (dtbpe)Ni鈺怤{2,6-iPr₂C₆H₃}, are also reported with small, unsaturated molecules such as diphenylketene, benzylisocyanate, benzaldehyde, and carbon dioxide, including the formation of C鈥揘 and N鈥揘 bonds by coupling reactions. In addition to NMR spectroscopic data and combustion analysis, we also report structural studies for all the cycloaddition reactions involving the imido (dtbpe)Ni鈺怤{2,6-iPr₂C₆H₃}.}