A Two-Step Catalytic Cycle for the Acceptorless Dehydrogenation of Ethane by Group 10 Metal Complexes: Role of the Metal in Reactivity and Selectivity
Author ORCID Identifier
Kevin Parker:https://orcid.org/0000-0002-8505-8468
Victor Ryzhov:https://orcid.org/0000-0001-6041-9821
Publication Title
Organometallics
ISSN
02767333
E-ISSN
15206041
Document Type
Article
Abstract
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.
First Page
4027
Last Page
4036
Publication Date
11-23-2020
DOI
10.1021/acs.organomet.0c00598
Recommended Citation
Parker, Kevin; Weragoda, Geethika K.; Canty, Allan J.; Polyzos, Anastasios; Ryzhov, Victor; and O'Hair, Richard A.J., "A Two-Step Catalytic Cycle for the Acceptorless Dehydrogenation of Ethane by Group 10 Metal Complexes: Role of the Metal in Reactivity and Selectivity" (2020). NIU Bibliography. 281.
https://huskiecommons.lib.niu.edu/niubib/281
Department
Department of Chemistry and Biochemistry
