Two new pyrazine-bridged, linear chain complexes of Cu(II) of formula [Cu(pzdo)2(H2O)2(pz)](A)2·nH2O [pzdo = pyrazine-N,N′-dioxide; pz = pyrazine; A = BF4− (1), ClO4− (2)] have been prepared. Single-crystal X-ray diffraction shows the Cu ions to be six-coordinate, pyrazine-bridged chains with trans-pairs of ancillary ligands. The pzdo molecules are coordinated through their oxygen atoms. The ClO4− and BF4− anions are each two-site disordered in the lattice. Further, there are partial occupancy water molecules in the lattice which are very weakly bound. The structures are stabilized by hydrogen bonds between the coordinated water molecules and the non-coordinated pzdo oxygen atoms as well as the anions. Variable temperature magnetic susceptibility data show antiferromagnetic interactions and the data were fit to the uniform chain model yielding J/kB = −13.0(2) K and −11.8(2) K for 1 and 2, respectively []. In addition, the structure of the serendipitously prepared compound [Cu(pz)(pzdo)(H2O)2](ClO4)2 (3) is described. The compound crystallizes as rectangular layers of Cu(II) ions bridged by pzdo (parallel to the a-axis) and pyrazine (parallel to the b-axis) with water molecules coordinated in the axial sites.

We report a new terpyridine-based FeN₃O catalyst, Fe(tpy^tbupho)Cl₂, which reduces O₂ to H₂O. Variable concentration and variable temperature spectrochemical studies with decamethylferrocene as a chemical reductant in acetonitrile solution enabled the elucidation of key reaction parameters for the catalytic reduction of O₂ to H₂O by Fe(tpy^tbupho)Cl₂. These mechanistic studies suggest that a 2 + 2 mechanism is operative, where hydrogen peroxide is produced as a discrete intermediate, prior to further reduction to H₂O. Consistent with this proposal, the spectrochemically measured first-order rate constant k (s⁻¹) value for H₂O₂ reduction is larger than that for O₂ reduction. Further, significant H₂O₂ production is observed under hydrodynamic conditions in rotating ring-disk electrode measurements, where the product can be swept away from the cathode surface before further reduction occurs.

A novel process is described for the synthesis of di- and trisubstituted cyclohexenes from an arene. These compounds are prepared from three independent nucleophilic addition reactions to a phenyl sulfone (PhSO₂R; R = Me, Ph, and NC₄H₈) dihapto-coordinated to the tungsten complex {WTp(NO)(PMe₃)}(Tp = trispyrazolylborate). Such a coordination renders the dearomatized aryl ring susceptible to protonation at a carbon ortho to the sulfone group. The resulting arenium species readily reacts with the first nucleophile to form a dihapto-coordinated sulfonylated diene complex. This complex can again be protonated, and the subsequent nucleophilic addition forms a trisubstituted cyclohexene species bearing a sulfonyl group at an allylic position. Loss of the sulfinate anion forms a π-allyl species, to which a third nucleophile can be added. The trisubstituted cyclohexene can then be oxidatively decomplexed, either before or after substitution of the sulfonyl group. Nucleophiles employed include masked enolates, cyanide, amines, amides, and hydride, with all three additions occurring to the same face of the ring, anti to the metal. Of the 12 novel functionalized cyclohexenes prepared as examples of this methodology, nine compounds meet five independent criteria for evaluating drug likeliness. Structural assignments are supported with nine crystal structures, density functional theory studies, and full 2D NMR analysis.

The catalytic partial oxidation of methane is achieved at low temperatures (<200 °C) using manganese oxides and manganese salts in mixtures of trifluoroacetic acid and trifluoroacetic anhydride. Dioxygen is used as the in situ terminal oxidant. For Mn oxides (e.g., MnO₂, Mn₂O₃, and Mn₃O₄), we studied stoichiometric methane partial oxidation in HTFA (TFA = trifluoroacetate). Using a Mn trifluoroacetate salt, at 180 °C and under 25 psig of methane, product selectivity for the mono-oxidized product methyl trifluoroacetate (MeTFA) is observed to be >90% at ∼35% methane conversion at approximately 6 turnovers. Under our catalytic methane oxidation reaction conditions, MeTFA is stable against overoxidation, which explains the likely high selectivity at conversions >15%. Using combined experimental studies and DFT calculations, a mechanism involving soluble and molecular Mn species in the catalytic cycle is proposed. The proposed reaction pathway involves initial activation of Mn^II by dioxygen, cleavage of a methane C–H bond by a Mn^III hydroxo intermediate, rebound of the methyl radical to generate MeTFA, and finally regeneration of the starting Mn^II complex. Also, this process is shown to be applicable to the oxidation of ethane, favoring the mono-oxidized product ethyl trifluoroacetate (EtTFA) and reaching ∼46% conversion.

Borepin, a 7-membered boron-containing heterocycle, has become an emerging molecular platform for the development of new materials and optoelectronics. While neutral borepins are well-established, reduced borepin species have remained elusive. Herein we report the first isolable, crystalline borepin radicals ( 2a , 2b ) and anions ( 3a , 3b ), which have been synthesized by potassium graphite (KC₈) reduction of dibenzo[b,d]borepin in the presence of free cyclic(alkyl)(amino) carbene. Borepin radicals and anions have been characterized by EPR or NMR, elemental analysis, X-ray crystallography and cyclic voltammetry. In addition, the bonding features have been investigated computationally using density functional theory.