Functionalization of Rhenium Aryl Bonds by O-Atom Transfer

Abstract

S2General Procedures: All manipulations were carried out using an argon filled MBraun glovebox and standard Schlenk techniques using over dried glassware (>1 h at 110 °C under vacuum,. THF was HPLC grade from EMD and distilled over Na/Benzophenone and then degassed under argon before use. H 2 O was degassed and stored under argon before use.Pentane was HPLC grade from EMD and distilled over NaH prior to use. Reagent-grade chemicals and solvents were purchased from Sigma Aldrich, Alfa Aesar, or EMD and used as is unless otherwise specified. Deuterated solvents were purchased from Cambridge Isotope Inc. and degassed and stored under argon before use. Re 2 O 7 was obtained from Strem or Alfa and stored in the glovebox freezer (-30 °C) before use. H 2 18 O 2 was obtained from Sigma Aldrich. H 2 18 O was obtained from Cambridge Isotopes Inc. Elemental analyses were performed by Columbia Analytical Services; Tucson, Arizona. Electrospray Ionization (ESI) mass spectroscopy was performed at the University of Florida Mass Spec Facility; Gainesville, Florida. Liquid phase organic products were analyzed with a Shimadzu GC-MS QP2010S equipped with cross-linked methyl silicone gum capillary column, RTX-5. Gas measurements were performed using an Agilent GasPro column. The retention times of the products were confirmed by known standards. NMR spectra were obtained on a Bruker Digital Avance III 400 (400.132 MHz for 1 H and 100.623 MHz for 13 C) spectrometer. Chemical shifts are given in ppm relative to residual solvent proton resonances or to a stated internal or external standard. The rhenium phenyl, tolyl,pentafluoro, and mesityl trioxides have been previously prepared and characterization data of these compounds compared with that of previous reports. 1 The phenyl and pentafluoro diarylzincs were purchased from Strem Inc. The tolyl 2 and mesityl 3 diaryl-zincs were prepared as previously described.

Jaguar: A high‐performance quantum chemistry software program with strengths in life and materials sciences

“…Jaguar has been used extensively to study a wide range of homogeneous catalytic systems. Examples include Ru‐alkylidene catalysts for enyne metathesis, Ir(III) CO 2 hydrogenation catalysts, CH bond activation by Pt, Ir, and Os complexes, dioxirane‐catalyzed asymmetric epoxidations, Pd‐monophosphine catalysts for Suzuki–Miyaura coupling, Au(I) catalysts, oxy‐functionalization of ReC bonds, and Pd oxidation catalysts …”

The para-substituent effect and pH-dependence of the organometallic Baeyer–Villiger oxidation of rhenium–carbon bonds

“…More recently, we studied the oxidation of 2,4,6-trimethylphenylrhenium trioxide (Mes-ReO 3 , MesTO) in similar conditions. 4 We found that the lowest-barrier pathway is also through a BV type oxygen insertion, and that the replacement of alkyl by aryl migrating groups leads to an increase in the reaction rate.…”

“…Facile oxy-functionalization reactions of nucleophilic M δ+ -R δ− complexes are rare, [1][2][3][4][5] although functionalizations are well-known for M δ− -R δ+ intermediates of more electronegative metals. [6][7][8] Some of us reported recently both theory and experiments on the reaction of methylrhenium trioxide (CH 3 -ReO 3 , MTO) with oxidants (H 2 O 2 , PhIO, and IO 4 − ) in the aqueous phase.…”

Electrophilic RhI catalysts for arene H/D exchange in acidic media: Evidence for an electrophilic aromatic substitution mechanism

“…Developing reactivity with earlier transition metals (i.e., earlier than the Ni, Pd and Pt triad) could provide more tolerance of Lewis basic groups, but major challenges include avoiding oxidation of the metal to higher valent states that are incapable of C-H activation and developing complexes that possess electrophilic hydrocarbyl ligands (after C-H activation) [42][43][44][45][46][47][48][49][50][51][52][53]. Recently, a number of catalysts based on Ir and Rh have been shown to be active for benzene C−H activation [50][51][52][53][54][55][56][57][58][59][60][61].…”