Syntheses
of a Novel Fluorinated Trisphosphinoborate
Ligand and Its Copper and Silver Complexes. Catalytic Activity toward
Nitrene Transfer Reactions
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Abstract
A novel
fluorinated ligand, the anionic PhB(CH<sub>2</sub>P(<i>p</i>-CF<sub>3</sub>C<sub>6</sub>H<sub>4</sub>)<sub>2</sub>)<sub>3</sub> (PhBP<sub>3</sub> <sup><i>p</i>‑CF3Ph</sup>), has
been synthesized and characterized, as well as its corresponding thallium,
copper, and silver derivatives. The presence of fluorine atoms in
the ligand structure induced the desired effect of enhancing electrophilic
character at the metal center, without promoting substantial changes
in the ligand skeleton compared with the parent ligand PhB(CH<sub>2</sub>PPh<sub>2</sub>)<sub>3</sub><sup>−</sup> (PhBP<sub>3</sub>). Olefin aziridination
and C–H amidation reactions have been induced with those complexes
as catalyst precursors. The copper derivative catalyzed the olefin
aziridination of an array of olefins bearing either electron-donating
or electron-withdrawing groups. The silver analogue was found to promote
the C–H amidation of a series of substrates in moderate to
high yields
