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Cracking and dehydrogenation of cyclohexane by [(phen)M(X)]+ (M = Ni, Pd, Pt; X = H, CH3) in the gas phase

Parker, K, Weragoda, GK, Mohr, A, Canty, AJ, O'Hair, RAJ and Ryzhov, V 2021 , 'Cracking and dehydrogenation of cyclohexane by [(phen)M(X)]+ (M = Ni, Pd, Pt; X = H, CH3) in the gas phase' , Organometallics, vol. 40, no. 19 , pp. 3351-3359 , doi: 10.1021/acs.organomet.1c00467.

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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: Article
Authors/Creators:Parker, K and Weragoda, GK and Mohr, A and Canty, AJ and O'Hair, RAJ and Ryzhov, V
Keywords: organopalladium, gas phase chemistry, organometallic mechanisms, DFT, mass spectrometry, gas phase catalysis, CH activation, naphthene chemistry
Journal or Publication Title: Organometallics
Publisher: Amer Chemical Soc
ISSN: 0276-7333
DOI / ID Number: 10.1021/acs.organomet.1c00467
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© 2021 American Chemical Society

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