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Catalytic Methane Monofunctionalization by an Electrogenerated High-Valent Pd Intermediate.

ABSTRACT: Electrophilic high-valent metal ions are potent intermediates for the catalytic functionalization of methane, but in many cases, their high redox potentials make these intermediates difficult or impossible to access using mild stoichiometric oxidants derived from O2. Herein, we establish electrochemical oxidation as a versatile new strategy for accessing high-valent methane monofunctionalization catalysts. We provide evidence for the electrochemical oxidation of simple PdSO4 in concentrated sulfuric acid electrolytes to generate a putative Pd2III,III species in an all-oxidic ligand field. This electrogenerated high-valent Pd complex rapidly activates methane with a low barrier of 25.9 (±2.6) kcal/mol, generating methanol precursors methyl bisulfate (CH3OSO3H) and methanesulfonic acid (CH3SO3H) via concurrent faradaic and nonfaradaic reaction pathways. This work enables new electrochemical approaches for promoting rapid methane monofunctionalization.

SUBMITTER: O'Reilly ME

PROVIDER: S-EPMC5704285 | biostudies-literature | 2017 Nov

REPOSITORIES: biostudies-literature

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Catalytic Methane Monofunctionalization by an Electrogenerated High-Valent Pd Intermediate.

O'Reilly Matthew E ME Kim R Soyoung RS Oh Seokjoon S Surendranath Yogesh Y

ACS central science 20171012 11

Electrophilic high-valent metal ions are potent intermediates for the catalytic functionalization of methane, but in many cases, their high redox potentials make these intermediates difficult or impossible to access using mild stoichiometric oxidants derived from O<sub>2</sub>. Herein, we establish electrochemical oxidation as a versatile new strategy for accessing high-valent methane monofunctionalization catalysts. We provide evidence for the electrochemical oxidation of simple PdSO<sub>4</sub ...[more]

PMID: 29202019

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Project description:A temperature induced valence phase transition from Yb3+ at higher temperatures to Yb2+ at lower temperatures was observed at T = 110(1) K for intermetallic YbPd2Al3. The title compound has been prepared from the elements in sealed tantalum ampoules. The structure was refined from single-crystal data and the title compound was found to crystallize in the hexagonal YNi2Al3 type structure with space group P6/mmm and lattice parameters of a = 929.56(7) and c = 420.16(3) pm (300 K data). Full ordering of the Pd and Al atoms within the [Pd2Al3] δ- polyanion was observed. Magnetic measurements revealed an anomaly in the dc susceptibility data and intermediate valent Yb at higher temperature, as observed from the effective magnetic moment. The proposed valence phase transition was also observed as a λ-type anomaly in heat capacity measurements (T = 108.4(1) K), however, no systematic shift of the λ-peak was observed in field dependent heat capacity measurements. An antiferromagnetic ordering at this temperature, however, could be excluded, based on field-dependent susceptibility measurements and magnetization isotherms. No dynamic phenomenon was observed in ac susceptibility measurements, excluding e.g. spin-glass behavior. Subsequent temperature dependent single-crystal and powder X-ray diffraction experiments indicated a steep increase in the length of the c axis around T = 110 K upon cooling. However, no structural phase transition was found via single-crystal diffraction experiments conducted at 90 K. The anomaly was also observed in other physical measurements of e.g. the electrical resistivity, indicating a clear change in the electronic structure of the material. X-ray photoelectron spectroscopy conducted at room temperature shows the presence of both, Yb2+ and Yb3+, underlining the mixed-valent state. Members of the solid solution Yb1-x Ca x Pd2Al3 (x = 0.33, 0.67, 1) were finally used to further study the charge ordering and the present temperature induced valence phase transition.

Dataset Information

Catalytic Methane Monofunctionalization by an Electrogenerated High-Valent Pd Intermediate.

Publications

Catalytic Methane Monofunctionalization by an Electrogenerated High-Valent Pd Intermediate.

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