Reductive functionalization of a rhodium(III)-methyl bond in acidic media: Key step in the electrophilic functionalization of methane

Matthew E. O'Reilly, Dale R. Pahls, Thomas R. Cundari, T. Brent Gunnoe

Research output: Contribution to journalArticlepeer-review

12 Scopus citations

Abstract

The reductive functionalization of RhIII-Me bonds in acids is a key step for RhI/III-based catalysts for methane functionalization. Heating electronic-rich [tBu3terpy]Rh(Me)(Cl)I (1; tBu3terpy = 4,4′,4′-tri-tert-butylterpyridine) in H2O, AcOD, or trifluoroacetic acid (HTFA) released a stoichiometric amount of methane. With use of a less donating ligand, [(NO2)3terpy]Rh(Me)(Cl)I (2; (NO2)3terpy = 4,4′,4′-trinitroterpyridine), a mixture of CH4 and CH3X (X = Cl, TFA, OAc, OH) was obtained. The selectivity between MeX and CH4 was found to be dependent on the halide present (I- or Cl-). In a key experiment with the removal of one halide from 2, {[(NO2)3terpy]Rh(Me)Cl}{BF4} (3) was completely protonated in acidic solvent. DFT calculations were employed to investigate the mechanism of reductive functionalization and protonation.

Original languageEnglish (US)
Pages (from-to)6504-6510
Number of pages7
JournalOrganometallics
Volume33
Issue number22
DOIs
StatePublished - Nov 24 2014

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