2 research outputs found
Catalytic Arene H/D Exchange with Novel Rhodium and Iridium Complexes
Three novel pendant acetate complexes, [RhÂ(bdmpza)ÂCl<sub>3</sub>]<sup>−</sup>M<sup>+</sup>, [RhÂ(bdmpza)ÂCl<sub>2</sub>(py)],
and [IrÂ(bdmpza)ÂCl<sub>3</sub>]<sup>−</sup>M<sup>+</sup> (bdmpza
= bisÂ(3,5-dimethylpyrazol-1-yl) acetate, M<sup>+</sup> = Li<sup>+</sup>, Na<sup>+</sup>), were synthesized. Abstraction of halide from these
complexes with silver salts yielded species capable of C–H
activation of arenes. The catalytic H/D exchange reaction between
benzene and trifluoroacetic acid-<i>d</i><sub></sub> was
optimized, and these conditions were used to evaluate H/D exchange
in other arenes. Branched alkyl substituents in alkyl aromatics showed
an affinity toward deuterium exchange in the β-alkyl position
only. DFT calculations were performed to determine the mechanism of
H/D exchange
Catalytic Arene H/D Exchange with Novel Rhodium and Iridium Complexes
Three novel pendant acetate complexes, [RhÂ(bdmpza)ÂCl<sub>3</sub>]<sup>−</sup>M<sup>+</sup>, [RhÂ(bdmpza)ÂCl<sub>2</sub>(py)],
and [IrÂ(bdmpza)ÂCl<sub>3</sub>]<sup>−</sup>M<sup>+</sup> (bdmpza
= bisÂ(3,5-dimethylpyrazol-1-yl) acetate, M<sup>+</sup> = Li<sup>+</sup>, Na<sup>+</sup>), were synthesized. Abstraction of halide from these
complexes with silver salts yielded species capable of C–H
activation of arenes. The catalytic H/D exchange reaction between
benzene and trifluoroacetic acid-<i>d</i><sub></sub> was
optimized, and these conditions were used to evaluate H/D exchange
in other arenes. Branched alkyl substituents in alkyl aromatics showed
an affinity toward deuterium exchange in the β-alkyl position
only. DFT calculations were performed to determine the mechanism of
H/D exchange