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Cracking and dehydrogenation of cyclohexane by [(phen)M(X)]+ (M = Ni, Pd, Pt; X = H, CH3) in the gas phase
journal contribution
posted on 2023-05-21, 04:03 authored by Parker, K, Weragoda, GK, Mohr, A, Allan CantyAllan Canty, O'Hair, RAJ, Ryzhov, VGas-phase cationic ternary complexes of group 10 metals of the formula [(phen)M(X)]+, where phen = 1,10-phenanthroline (M = Ni, Pd, or Pt; and X = H or CH3), react with cyclohexane via C–H activation, forming the respective cyclohexyl species [(phen)M(c-C6H11)]+. Upon collisional activation, these species undergo two key competing processes: (i) ring opening followed by “cracking” of the hydrocarbon chain leading to extrusion of propylene and ethylene as major products among other hydrocarbons; and (ii) dehydrogenation of the cyclohexyl ring leading to the loss of one, two, or three hydrogen molecules, with subsequent loss of cyclohexenes or benzene. The relative prevalence of these two pathways strongly depends on the metal ion, with Pt preferring dehydrogenation over ring opening. The multiple catalytic cycles operating within both pathways are described. Density functional theory (DFT) calculations are used to shed light on mechanistic aspects associated with the experimental results.
History
Publication title
OrganometallicsVolume
40Issue
19Pagination
3351-3359ISSN
0276-7333Department/School
School of Natural SciencesPublisher
Amer Chemical SocPlace of publication
1155 16Th St, Nw, Washington, USA, Dc, 20036Rights statement
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