Net reductive elimination (RE) of MeX (X = halide or pseudo-halide: Cl(-), CF3CO2(-), HSO4(-), OH(-)) is an important step during Pt-catalyzed hydrocarbon functionalization. Developing Rh(I/III)-based catalysts for alkane functionalization is an attractive alternative to Pt-based systems, but very few examples of RE of alkyl halides and/or pseudo-halides from Rh(III) complexes have been reported. Here, we compare the influence of the ligand donor strength on the thermodynamic potentials for oxidative addition and reductive functionalization using [(t)Bu3terpy]RhCl (1) {(t)Bu3terpy = 4,4',4''-tri-tert-butylpyridine} and [(NO2)3terpy]RhCl (2) {(NO2)3terpy = 4,4',4''-trinitroterpyridine}. Complex 1 oxidatively adds MeX {X = I(-), Cl(-), CF3CO2(-) (TFA(-))} to afford [(t)Bu3terpy]RhMe(Cl)(X) {X = I(-) (3), Cl(-) (4), TFA(-) (5)}. By having three electron-withdrawing NO2 groups, complex 2 does not react with MeCl or MeTFA, but reacts with MeI to yield [(NO2)3terpy]RhMe(Cl)(I) (6). Heating 6 expels MeCl along with a small quantity of MeI. Repeating this experiment but with excess [Bu4N]Cl exclusively yields MeCl, while adding [Bu4N]TFA yields a mixture of MeTFA and MeCl. In contrast, 3 does not reductively eliminate MeX under similar conditions. DFT calculations successfully predict the reaction outcome by complexes 1 and 2. Calorimetric measurements of [(t)Bu3terpy]RhI (7) and [(t)Bu3terpy]RhMe(I)2 (8) were used to corroborate computational models. Finally, the mechanism of MeCl RE from 6 was investigated via DFT calculations, which supports a nucleophilic attack by either I(-) or Cl(-) on the Rh-CH3 bond of a five-coordinate Rh complex.
This research output has an Altmetric Attention Score of 4. This is our high-level measure of the quality and quantity of online attention that it has received. This Attention Score, as well as the ranking and number of research outputs shown below, was calculated when the research output was last mentioned on 29 September 2016.
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#3,931
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So far Altmetric has tracked 24,773 research outputs from this source. They receive a mean Attention Score of 2.4. This one has done well, scoring higher than 78% of its peers.
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