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Direct Manipulation of Metal Imido Geometry: Key Principles to Enhance C-H Amination Efficacy.


ABSTRACT: We report the catalytic C-H amination mediated by an isolable CoIII imido complex (TrL)Co(NR) supported by a sterically demanding dipyrromethene ligand (TrL = 5-mesityl-1,9-(trityl)dipyrrin). Metalation of (TrL)Li with CoCl2 in THF afforded a high-spin (S = 3/2) three-coordinate complex (TrL)CoCl. Chemical reduction of (TrL)CoCl with potassium graphite yielded the high-spin (S = 1) CoI synthon (TrL)Co which is stabilized through an intramolecular ?6-arene interaction. Treatment of (TrL)Co with a stoichiometric amount of 1-azidoadamantane (AdN3) furnished a three-coordinate, diamagnetic CoIII imide (TrL)Co(NAd) as confirmed by single-crystal X-ray diffraction, revealing a rare trigonal pyramidal geometry with an acute Co-Nimido-C angle 145.0(3)°. Exposure of 1-10 mol % of (TrL)Co to linear alkyl azides (RN3) resulted in catalytic formation of substituted N-heterocycles via intramolecular C-H amination of a range of C-H bonds, including primary C-H bonds. The mechanism of the C-N bond formation was probed via initial rate kinetic analysis and kinetic isotope effect experiments [kH/kD = 38.4(1)], suggesting a stepwise H-atom abstraction followed by radical recombination. In contrast to the previously reported C-H amination mediated by (ArL)Co(NR) (ArL = 5-mesityl-1,9-(2,4,6-Ph3C6H2)dipyrrin), (TrL)Co(NR) displays enhanced yields and rates of C-H amination without the aid of a cocatalyst, and no catalyst degradation to a tetrazene species was observed, as further supported by the pyridine inhibition effect on the rate of C-H amination. Furthermore, (TrL)Co(NAd) exhibits an extremely low one-electron reduction potential (E°red = -1.98 V vs [Cp2Fe]+/0) indicating that the highly basic terminal imido unit contributes to the driving force for H-atom abstraction.

SUBMITTER: Baek Y 

PROVIDER: S-EPMC7262787 | biostudies-literature | 2019 Oct

REPOSITORIES: biostudies-literature

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Direct Manipulation of Metal Imido Geometry: Key Principles to Enhance C-H Amination Efficacy.

Baek Yunjung Y   Hennessy Elisabeth T ET   Betley Theodore A TA  

Journal of the American Chemical Society 20191010 42


We report the catalytic C-H amination mediated by an isolable Co<sup>III</sup> imido complex (<sup>Tr</sup>L)Co(NR) supported by a sterically demanding dipyrromethene ligand (<sup>Tr</sup>L = 5-mesityl-1,9-(trityl)dipyrrin). Metalation of (<sup>Tr</sup>L)Li with CoCl<sub>2</sub> in THF afforded a high-spin (<i>S</i> = 3/2) three-coordinate complex (<sup>Tr</sup>L)CoCl. Chemical reduction of (<sup>Tr</sup>L)CoCl with potassium graphite yielded the high-spin (<i>S</i> = 1) Co<sup>I</sup> synthon (  ...[more]

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