Product Protection, the Key to Developing High Performance Methane Selective Oxidation Catalysts

Selective, direct conversion of methane to methanol might seem an impossible task since the C−H bond energy of methane is 105 kcal mol^(−1) compared to the C−H bond energy for methanol of 94. We show here that the Catalytica catalyst is successful because the methanol is protected as methyl bisulfate, which is substantially less reactive than methanol toward the catalyst. This analysis suggests a limiting performance for systems that operate by this type of protection that is well above the Catalytica system

C–H activation in strongly acidic media. The co-catalytic effect of the reaction medium

Quantum mechanical (QM) results are used to establish the role of sulfuric acid solvent in facilitating the reaction between Pt^(II)(bpym)Cl_2 (bpym = 2,2'-bipyrimidinyl) and methane; coordination of methane to the platinum catalyst is found to be catalyzed by the acidic mediu

C-H activation in strongly acidic media. The co-catalytic effect of the reaction medium

Quantum mechanical (QM) results are used to establish the role of sulfuric acid solvent in facilitating the reaction between Pt^(II)(bpym)Cl_2 (bpym = 2,2'-bipyrimidinyl) and methane; coordination of methane to the platinum catalyst is found to be catalyzed by the acidic medium

Carbon−Oxygen Bond Forming Mechanisms in Rhenium Oxo-Alkyl Complexes

Three C−X bond formation mechanisms observed in the oxidation of (HBpz_3)ReO(R)(OTf) [HBpz_3 = hydrotris(1-pyrazolyl)borate; R = Me, Et, and iPr; OTf = OSO_2CF_3] by dimethyl sulfoxide (DMSO) were investigated using quantum mechanics (M06//B3LYP DFT) combined with solvation (using the PBF Poisson−Boltzmann polarizable continuum solvent model). For R = Et we find the alkyl group is activated through α-hydrogen abstraction by external base OTf^− with a free energy barrier of only 12.0 kcal/mol, leading to formation of acetaldehyde. Alternatively, ethyl migration across the M═O bond (leading to the formation of acetaldehyde and ethanol) poses a free energy barrier of 22.1 kcal/mol, and the previously proposed α-hydrogen transfer to oxo (a 2+2 forbidden reaction) poses a barrier of 44.9 kcal/mol. The rate-determining step to formation of the final product acetaldehyde is an oxygen atom transfer from DMSO to the ethylidene, with a free energy barrier of 15.3 kcal/mol. When R = iPr, the alkyl 1,2-migration pathway becomes the more favorable pathway (both kinetically and thermodynamically), with a free energy barrier (ΔG^‡ = 11.8 kcal/mol) lower than α-hydrogen abstraction by OTf^− (ΔG^‡ = 13.5 kcal/mol). This suggests the feasibility of utilizing this type of migration to functionalize M−R to M−OR. We also considered the nucleophilic attack of water and ammonia on the Re-ethylidene α-carbon as a means of recovering two-electron-oxidized products from an alkane oxidation. Nucleophilic attack (with internal deprotonation of the nucleophile) is exothermic. However, the subsequent protonolysis of the Re−alkyl bond (to liberate an alcohol or amine) poses a barrier of 37.0 or 42.4 kcal/mol, respectively. Where comparisons are possible, calculated free energies agree very well with experimental measurements

Preparation of potentially porous, chiral organometallic materials through spontaneous resolution of pincer palladium conformers

Understanding the mechanism by which advanced materials assemble is essential for the design of new materials with desired properties. Here, we report a method to form chiral, potentially porous materials through spontaneous resolution of conformers of a PCP pincer palladium complex ({; ; 2, 6-bis[(di-t-butylphosphino)methyl]phenyl}; ; palladium(II)halide). The crystallisation is controlled by weak hydrogen bonding giving rise to chiral qtz-nets and channel structures, as shown by 16 such crystal structures for X = Cl, and Br with various solvents like pentane and bromobutane. The fourth ligand (in addition to the pincer ligand) on palladium plays a crucial role ; the chloride and the bromide primarily form hexagonal crystals with large 1D channels, whereas the iodide (presumably due to its inferior hydrogen bonding capacity) forms monoclinic crystals without channels. The hexagonal channels are completely hydrophobic and filled with disordered solvent molecules. Upon heating loss of solvent occurs and the hexagonal crystals transform into other non-porous polymorphs. Also by introducing strong acid, the crystallisation process can be directed to a different course, giving several different non-porous polymorphs. In conclusion a number of rules can be formulated dictating the formation of hexagonal channel structures based on pincer palladium complexes. Such rules are important for a rational design of future self-assembling materials with applications in storage and molecular recognition

Using Reduced Catalysts for Oxidation Reactions: Mechanistic Studies of the “Periana-Catalytica” System for CH_4 Oxidation

Designing oxidation catalysts based on CH activation with reduced, low oxidation state species is a seeming dilemma given the proclivity for catalyst deactivation by overoxidation. This dilemma has been recognized in the Shilov system where reduced Pt^(II) is used to catalyze methane functionalization. Thus, it is generally accepted that key to replacing Pt^(IV) in that system with more practical oxidants is ensuring that the oxidant does not over-oxidize the reduced Pt^(II) species. The “Periana-Catalytica” system, which utilizes (bpym)Pt^(II)Cl_2 in concentrated sulfuric acid solvent at 200 °C, is a highly stable catalyst for the selective, high yield oxy-functionalization of methane. In lieu of the over-oxidation dilemma, the high stability and observed rapid oxidation of (bpym)Pt^(II)Cl_2 to Pt^(IV) in the absence of methane would seem to contradict the originally proposed mechanism involving CH activation by a reduced Pt^(II) species. Mechanistic studies show that the originally proposed mechanism is incomplete and that while CH activation does proceed with Pt^(II) there is a solution to the over-oxidation dilemma. Importantly, contrary to the accepted view to minimize Pt^(II) overoxidation, these studies also show that increasing that rate could increase the rate of catalysis and catalyst stability. The mechanistic basis for this counterintuitive prediction could help to guide the design of new catalysts for alkane oxidation that operate by CH activation