Gas-phase cationic ternary complexes of group 10 metals of the formula [(phen)M(X)] + , where phen = 1,10phenanthroline (M = Ni, Pd, or Pt; and X = H or CH 3 ), react with cyclohexane via C−H activation, forming the respective cyclohexyl species [(phen)M(c-C 6 H 11 )] + . 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.
Two rare earth oxysulfides Ln
5V3O7S6 (Ln = La, Ce) have been synthesized and their structures determined. The two isostructural compounds crystallize in the orthorhombic space group Pmmn (no. 59). The structure features one-dimensional edge-sharing VS4O2 octahedron chains parallel to the b axis. The bonding between V and S/O is covalent, and between Ln
3+ and the rest of the matrix ionic. Magnetic susceptibility measurement revealed that V is in a mixed valence state of V3+ and V4+. Its magnetic behavior follows the Curie-Weiss law.
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