Reductive functionalization of a rhodium(III)- methyl bond by electronic modification of the supporting ligand

Matthew E. OReilly; Dale R. Pahls; Joanna R. WebbNicholas C. BoazSubhojit MajumdarCarl D. HoffJohn T. GrovesThomas R. CundariT. Brent Gunnoe

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Reductive functionalization of a rhodium(III)- methyl bond by electronic modification of the supporting ligand

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Net reductive elimination (RE) of MeX (X = halide or pseudo-halide: Cl~?, CF_3CO_2~?, HSO_4~?, 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 tBu3terpyRhCl (1) {tBu3terpy = 4,4',4''-tri-tert-butylpyridine} and(NO_2)_3terpyRhCl (2) {(NO_2)_3terpy = 4,4',4''-trinitroterpyridine}. Complex 1 oxidatively adds MeX {X = I~?, Cl~?, CF_3CO_2~? (TFA~?)} to afford tBu3terpyRhMe(Cl)(X) {X = I~? (3), Cl~? (4), TFA~? (5)}. By having three electron- withdrawing NO_2 groups, complex 2 does not react with MeCl or MeTFA, but reacts with MeI to yield (NO_2)_3terpyRhMe(Cl)(I) (6). Heating 6 expels MeCl along with a small quantity of MeI. Repeating this experiment but with excess Bu_4NCl exclusively yields MeCl, while adding Bu_4NTFA 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~tBu_3terpyRhI (7) and ~tBu_3terpyRhMe(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-CH_3 bond of a five-coordinate Rh complex.

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来源
《Dalton transactions: An international journal of inorganic chemistry》 |2014年第22期|8273-8281|共9页
作者
Matthew E. OReilly; Dale R. Pahls; Joanna R. WebbNicholas C. BoazSubhojit MajumdarCarl D. HoffJohn T. GrovesThomas R. CundariT. Brent Gunnoe;
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作者单位

Department of Chemistry, University of Virginia, Charlottesville, Virginia 22904-4319, USA;

Department of Chemistry and Center for Advanced Scientific Computing and Modeling, University of North Texas, Denton, Texas 76203-5017, USA;

Department of Chemistry, Princeton University, Princeton, New Jersey 08544, USADepartment of Chemistry, University of Miami, 1301 Memorial Drive, Coral Gables, Florida 33146, USA;

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正文语种英语
中图分类化学;无机化学;
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Reductive; functionalization; a rhodium(III)- methyl;

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Reductive functionalization of a rhodium(III)- methyl bond by electronic modification of the supporting ligand

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