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Imine Nitrogen Bridged Binuclear Nickel Complexes via N–H Bond Activation: Synthesis, Characterization, Unexpected C,N-Coupling Reaction, and Their Catalytic Application in Hydrosilylation of Aldehydes
Abstract
The reactions of NiMe<sub>2</sub>(PMe<sub>3</sub>)<sub>3</sub> with 2,6-difluoroarylimines were explored. As a result, a series of binuclear nickel complexes (<b>5</b>–<b>8</b>,<b> 11</b>) were synthesized. Meanwhile, from the reactions of NiMe<sub>2</sub>(PMe<sub>3</sub>)<sub>3</sub> with [2-CH<sub>3</sub>C<sub>6</sub>H<sub>4</sub>-C(NH)-2,6-F<sub>2</sub>C<sub>6</sub>H<sub>3</sub>] (<b>9</b>) and [2,6-(CH<sub>3</sub>)<sub>2</sub>C<sub>6</sub>H<sub>3</sub>-C(NH)-2,6-F<sub>2</sub>C<sub>6</sub>H<sub>3</sub>] (<b>10</b>), two unexpected C,N-coupling products (<b>12</b> and <b>13</b>) were obtained. It is believed that these coupling reactions underwent activation of the N–H and C–F bonds. The binuclear nickel complexes showed excellent catalytic activity in the hydrosilylation of aldehydes. The mechanism of the reaction was studied through stoichiometric reactions, and the double-(η<sup>2</sup>-Si–H)–Ni<sup>II</sup> intermediate was detected by in situ <sup>1</sup>H NMR spectroscopy, which may be the key point in the catalytic cycle- Text
- Journal contribution
- Biophysics
- Biochemistry
- Medicine
- Sociology
- Biological Sciences not elsewhere classified
- Chemical Sciences not elsewhere classified
- 1 H NMR spectroscopy
- nickel complexes
- Imine Nitrogen Bridged Binuclear Nickel Complexes
- 3C
- Catalytic Application
- CH
- AldehydesThe reactions
- NiMe
- stoichiometric reactions