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Thermal Activation of CH 4 and H 2 as Mediated by the Ruthenium Oxide Cluster Ions [RuO x ] + ( x= 1–3): On the Influence of Oxidation States
Author(s) -
Sun Xiaoyan,
Zhou Shaodong,
Yue Lei,
Schlangen Maria,
Schwarz Helmut
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201806187
Subject(s) - ruthenium , chemistry , reactivity (psychology) , ruthenium oxide , oxide , cluster (spacecraft) , inorganic chemistry , crystallography , catalysis , medicine , biochemistry , alternative medicine , organic chemistry , pathology , computer science , programming language
Thermal gas‐phase reactions of the ruthenium‐oxide clusters [RuO x ] + ( x= 1–3) with methane and dihydrogen have been explored by using FT‐ICR mass spectrometry complemented by high‐level quantum chemical calculations. For methane activation, as compared to the previously studied [RuO] + /CH 4 couple, the higher oxidized Ru systems give rise to completely different product distributions. [RuO 2 ] + brings about the generations of [Ru,O,C,H 2 ] + /H 2 O, [Ru,O,C] + /H 2 /H 2 O, and [Ru,O,H 2 ] + /CH 2 O, whereas [RuO 3 ] + exhibits a higher selectivity and efficiency in producing formaldehyde and syngas (CO+H 2 ). Regarding the reactions with H 2 , as compared to CH 4 , both [RuO] + and [RuO 2 ] + react similarly inefficiently with oxygen‐atom transfer being the main reaction channel; in contrast, [RuO 3 ] + is inert toward dihydrogen. Theoretical analysis reveals that the reduction of the metal center drives the overall oxidation of methane, whereas the back‐bonding orbital interactions between the cluster ions and dihydrogen control the H−H bond activation. Furthermore, the reactivity patterns of [RuO x ] + ( x= 1–3) with CH 4 and H 2 have been compared with the previously reported results of Group 8 analogues [OsO x ] + /CH 4 /H 2 ( x= 1–3) and the [FeO] + /H 2 system. The electronic origins for their distinctly different reaction behaviors have been addressed.