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Selectivity of Rh???H-C Binding in a ?-Alkane Complex Controlled by the Secondary Microenvironment in the Solid State.

ABSTRACT: Single-crystal to single-crystal solid-state molecular organometallic (SMOM) techniques are used for the synthesis and structural characterization of the ?-alkane complex [Rh(tBu₂ PCH₂ CH₂ CH₂ PtBu₂ )(?² ,?² -C₇ H₁₂ )][BAr^F ₄ ] (Ar^F =3,5-(CF₃ )₂ C₆ H₃ ), in which the alkane (norbornane) binds through two exo-C-H???Rh interactions. In contrast, the bis-cyclohexyl phosphine analogue shows endo-alkane binding. A comparison of the two systems, supported by periodic DFT calculations, NCI plots and Hirshfeld surface analyses, traces this different regioselectivity to subtle changes in the local microenvironment surrounding the alkane ligand. A tertiary periodic structure supporting a secondary microenvironment that controls binding at the metal site has parallels with enzymes. The new ?-alkane complex is also a catalyst for solid/gas 1-butene isomerization, and catalyst resting states are identified for this.

SUBMITTER: Furfari SK

PROVIDER: S-EPMC7898853 | biostudies-literature | 2021 Feb

REPOSITORIES: biostudies-literature

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Selectivity of Rh⋅⋅⋅H-C Binding in a σ-Alkane Complex Controlled by the Secondary Microenvironment in the Solid State.

Furfari Samantha K SK Tegner Bengt E BE Burnage Arron L AL Doyle Laurence R LR Bukvic Alexander J AJ Macgregor Stuart A SA Weller Andrew S AS

Chemistry (Weinheim an der Bergstrasse, Germany) 20210112 9

Single-crystal to single-crystal solid-state molecular organometallic (SMOM) techniques are used for the synthesis and structural characterization of the σ-alkane complex [Rh(tBu2 PCH2 CH2 CH2 PtBu2 )(η2 ,η2 -C7 H12 )][BArF 4 ] (ArF =3,5-(CF3 )2 C6 H3 ), in which the alkane (norbornane) binds through two exo-C-H⋅⋅⋅Rh inter ...[more]

PMID: 33112000

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Project description:The non-oxidative catalytic dehydrogenation of light alkanes via C-H activation is a highly endothermic process that generally requires high temperatures and/or a sacrificial hydrogen acceptor to overcome unfavorable thermodynamics. This is complicated by alkanes being such poor ligands, meaning that binding at metal centers prior to C-H activation is disfavored. We demonstrate that by biasing the pre-equilibrium of alkane binding, by using solid-state molecular organometallic chemistry (SMOM-chem), well-defined isobutane and cyclohexane σ-complexes, [Rh(Cy2PCH2CH2PCy2)(η:η-(H3C)CH(CH3)2][BArF4] and [Rh(Cy2PCH2CH2PCy2)(η:η-C6H12)][BArF4] can be prepared by simple hydrogenation in a solid/gas single-crystal to single-crystal transformation of precursor alkene complexes. Solid-gas H/D exchange with D2 occurs at all C-H bonds in both alkane complexes, pointing to a variety of low energy fluxional processes that occur for the bound alkane ligands in the solid-state. These are probed by variable temperature solid-state nuclear magnetic resonance experiments and periodic density functional theory (DFT) calculations. These alkane σ-complexes undergo spontaneous acceptorless dehydrogenation at 298 K to reform the corresponding isobutene and cyclohexadiene complexes, by simple application of vacuum or Ar-flow to remove H2. These processes can be followed temporally, and modeled using classical chemical, or Johnson-Mehl-Avrami-Kologoromov, kinetics. When per-deuteration is coupled with dehydrogenation of cyclohexane to cyclohexadiene, this allows for two successive KIEs to be determined [kH/kD = 3.6(5) and 10.8(6)], showing that the rate-determining steps involve C-H activation. Periodic DFT calculations predict overall barriers of 20.6 and 24.4 kcal/mol for the two dehydrogenation steps, in good agreement with the values determined experimentally. The calculations also identify significant C-H bond elongation in both rate-limiting transition states and suggest that the large kH/kD for the second dehydrogenation results from a pre-equilibrium involving C-H oxidative cleavage and a subsequent rate-limiting β-H transfer step.

Project description:The well-defined particle morphology of crystalline MnWO4 catalysts investigated in the present study facilitates obtaining insight into the origin of selectivity limitations in alkane oxidation. Hydrothermal synthesis at variable pH values granted access to a series of phase-pure MnWO4 catalysts with particles ranging from cube-like (aspect ratio 1.5) to rod- or needle-like (aspect ratio 6.8) shapes. Kinetic studies reveal a strong dependence of the propane consumption rate on the particle shape. The true origin of the structure sensitivity was unraveled by comprehensive bulk and surface analysis using nitrogen adsorption, XRD, SEM, ADF-STEM, STEM-EELS, XPS, multi-laser excitation Raman and DRIFT/operando FTIR spectroscopies, temperature-programmed oxidation (TPO), in situ NEXAFS, and DFT calculations. The active phase is composed of a thin manganese oxy-hydroxide layer formed on the surface of crystalline MnWO4. The differences in catalytic performance within the series clearly illustrate that the structural motif as the most popular descriptor in oxidation catalysis is not essential, since all MnWO4 catalysts in the series under study exhibit the same bulk crystal structure and bulk chemical composition and are phase pure and homogenous. The variable particle shape serves as a proxy that reflects the formation of varying abundance of redox active Mn2+/Mn3+ surface sites, which correlates with catalytic activity. Operando FTIR spectroscopy directly confirms the formation of Mn-OH surface species by abstraction of hydrogen atoms from the propane molecule on nucleophilic oxygen atoms and suggests that active site regeneration occurs via oxidative dehydrogenation of Mn-OH species indicating a single-site nature of the active sites that does not allow four-electron reduction of molecular oxygen. Instead, intermediates are created that cause side reactions and lower the selectivity. The findings highlight fundamental design criteria that may be applied to advance the development of new alkane oxidation catalysts with improved selectivity.

Dataset Information

Selectivity of Rh???H-C Binding in a ?-Alkane Complex Controlled by the Secondary Microenvironment in the Solid State.

Publications

Selectivity of Rh⋅⋅⋅H-C Binding in a σ-Alkane Complex Controlled by the Secondary Microenvironment in the Solid State.

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