A Two-Step Catalytic Cycle for the Acceptorless Dehydrogenation of Ethane by Group 10 Metal Complexes: Role of the Metal in Reactivity and Selectivity
journal contributionposted on 13.11.2020, 09:05 by Kevin Parker, Geethika K. Weragoda, Allan J. Canty, Anastasios Polyzos, Victor Ryzhov, Richard A. J. O’Hair
Acceptorless dehydrogenation of ethane was achieved in the gas phase via a two-step catalytic cycle involving ternary cationic metal hydrides, [(phen)M(H)]+, 1, and metal ethides, [(phen)M(CH2CH3)]+, 2, (where M = Ni, Pd, or Pt, and phen = 1,10-phenanthroline). Species 1 and 2 were generated and their reactivity studied in a quadrupole ion trap mass spectrometer. It was found that 1 readily reacted with ethane releasing H2 and forming 2, with the relative reactivity being Pt > Ni ≫ Pd. Density functional theory (DFT) calculations for this metathesis reaction agree with the experimental reactivity order. Species 2 can in turn be converted into 1 and release ethylene when sufficient energy is supplied via collision-induced dissociation. DFT calculations also provided insight into competing side reactions (e.g., dehydrogenation of 2 and formation of protonated phen ligand) that become competitive during this endothermic step. The catalytic cycle can be repeated in the mass spectrometer several times. Multiple entry points into the cycle have been identified and discussed.
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Multiple entry pointsmetathesis reactionreactivity orderternary cationic metal hydridesrelease ethyleneGroup 10 Metal ComplexesPtPdprotonated phen ligandAcceptorless Dehydrogenationside reactionsSpecies 1H 2quadrupole ion trap mass spectrometerethaneSelectivity Acceptorless dehydrogen...NiCHcollision-induced dissociationmass spectrometergas phaseDFT calculationsmetal ethidesTwo-Step Catalytic Cyclespecies 2