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Rational Design of a Catalyst for the Selective Monoborylation of Methane

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Title
Rational Design of a Catalyst for the Selective Monoborylation of Methane
Author(s)
Seihwan Ahn; Sorsche, Dieter; Berrit, Simon; Gau, Michael R.; Mindiola, Daniel J.; Mu-Hyun Baik
Publication Date
2018-11
Journal
ACS CATALYSIS, v.8, no.11, pp.10021 - 10031
Publisher
AMER CHEMICAL SOC
Abstract
Combined computational and experimental studies elucidate the mechanism and suggest rational design and optimization strategies of a bis(phosphine)-supported iridium-catalyst for methane monoborylation. The activation of the C-H bond in methane via oxidative addition using tris(boryl) iridium(III) complexes bearing bis-chelating supporting ligands is modeled computationally. This model shows that the use of the soft Lewis base ligand such as 1,2-bis(dimethylphosphino)ethane (dmpe) lowers the activation barrier of the rate-determining step as it facilitates polarization of the metal-center, lowering the barrier of the oxidative addition to afford a seven-coordinate iridium(V) intermediate. The experimental optimization of this reaction using high-throughput methods shows that up to 170 turnovers can be achieved at 150 degrees C (500 psi) within 16 h using bis(pinacolato)diboron, a well-defined homogeneous and monomeric catalyst (dmpe)Ir(COD)Cl that is readily available from commercial precursors, with selectivity for the monoborylation product. High-boiling cyclic aliphatic solvents decalin and cyclooctane also prove suitable for this reaction, while being inert toward borylation. In accordance with the lower calculated activation barrier, catalytic turnover is also observed at 120 degrees C with up to 50 turnovers over the course of 4 days in cyclohexane solvent. It was found that the borylation of methane is only achieved via one catalytic cycle, and buildup of pinacolborane, a side-product from methane borylation with bis(pinacolato)diboron, inhibits catalytic activity.
URI
https://pr.ibs.re.kr/handle/8788114/9842
DOI
10.1021/acscatal.8b02771
ISSN
2155-5435
Appears in Collections:
Center for Catalytic Hydrocarbon Functionalizations(분자활성 촉매반응 연구단) > 1. Journal Papers (저널논문)
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