Gas-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.

Item Type:	Refereed Article
Keywords:	organopalladium, gas phase chemistry, organometallic mechanisms, DFT, mass spectrometry, gas phase catalysis, CH activation, naphthene chemistry
Research Division:	Chemical Sciences
Research Group:	Inorganic chemistry
Research Field:	Transition metal chemistry
Objective Division:	Expanding Knowledge
Objective Group:	Expanding knowledge
Objective Field:	Expanding knowledge in the physical sciences
UTAS Author:	Canty, AJ (Professor Allan Canty)
ID Code:	147691
Year Published:	2021
Web of Science® Times Cited:	4
Deposited By:	Chemistry
Deposited On:	2021-11-11
Last Modified:	2022-08-23
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