4.8 Article

Direct CO2 Addition to a Ni(0)-CO Species Allows the Selective Generation of a Nickel(II) Carboxylate with Expulsion of CO

期刊

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 140, 期 6, 页码 2179-2185

出版社

AMER CHEMICAL SOC
DOI: 10.1021/jacs.7b11074

关键词

-

资金

  1. C1 Gas Refinery Program through the National Research Foundation of Korea [NRF 2015M3D3A1A01064880, NRF-2015R1A2A2A01004197]
  2. National Research Foundation of Korea [2015R1A2A2A01004197, 2015M3D3A1A01064880] Funding Source: Korea Institute of Science & Technology Information (KISTI), National Science & Technology Information Service (NTIS)

向作者/读者索取更多资源

Addition of CO, to a low-valent nickel species has been explored with a newly designed (PNP)-P-acri pincer ligand ((PNP-)-P-acri = 4,5-bis(diisopropylphosphino)-2,7,9,9-tetramethyl-9H-acridin-10-ide). This is a crucial step in understanding biological CO2 conversion to CO found in carbon monoxide dehydrogenase (CODH). A four-coordinate nickel(0) state was reliably accessed in the presence of a CO ligand, which can be prepared from a stepwise reduction of a cationic {((PNP)-P-acri)Ni(II)-CO}(+) species. All three Ni(II), Ni(I), and Ni(0) monocarbonyl species were cleanly isolated and spectroscopically characterized. Addition of electrons to the nickel(II) species significantly alters its geometry from square planar toward tetrahedral because of the filling of the d(x)(-y)(2)(2) orbital. Accordingly, the CO ligand position changes from equatorial to axial, angle N-Ni-C of 176.2(2)degrees to 129.1(4)degrees, allowing opening of a CO, binding site. Upon addition of CO2 to a nickel(0) CO species, a nickel(II) carboxylate species with a Ni(eta(1)-CO2-KC) moiety was formed and isolated (75%). This reaction occurs with the concomitant expulsion of CO(g). This is a unique result markedly different from our previous report involving the flexible analogous PNP ligand, which revealed the formation of multiple products including a tetrameric cluster from the reaction with CO2. Finally, the carbon dioxide conversion to CO at a single nickel center is modeled by the successful isolation of all relevant intermediates, such as Ni-CO2, Ni-COOH, and Ni-CO.

作者

我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。

评论

主要评分

4.8
评分不足

次要评分

新颖性
-
重要性
-
科学严谨性
-
评价这篇论文

推荐

暂无数据
暂无数据