Die Chemie von [AuO]⁺/CH₄ in der Gasphase: Selektive Sauerstoffatom‐Übertragung auf, statt Wasserstoffatom‐Abstraktion von Methan

Abstract

Die thermischen Reaktionen von [AuO] + mit Methan wurden mittels FT-ICR-Massenspektrometrie und quantenchemischenRechnungen untersucht. Im Gegensatz zu den bereits untersuchten Oxiden der 11. Gruppe,[CuO] + und [AgO] + ,r eagiert [AuO] + mit CH 4 ausschließlich unter Bildung von CH 3 OH durchS auerstoffatomübertragung.D er neuartige Mechanismus dieser spezifischen Oxidation wird vorgestellt und die Ursachen der Trägheit des [AgO] + /CH 4 -Reaktionspaares mittels theoretischer Untersuchungen aufgedeckt.

Improving Transformations Through Organotrifluoroborates

“…A variety of 1-(hydroxy) alkyltrifluoroborates have been prepared from the corresponding aldehydes through a Cu-catalyzed diboration protocol employing ICyCuCl (ICy ¼ 1,3-dicyclohexylimidazol-2-ylidene) (Scheme 36) [73]. The developed method, which was based on a previously reported aldehyde diboration protocol [74], allows isolation of air-stable trifluoroborate salts upon quenching with KHF 2 . It was demonstrated that substrates bearing alkenes as well as protected alcohols and amines could be successfully prepared.…”

Probing Intermediates of Ion/Molecule Reactions by their Independent Gas‐Phase Synthesis and Fragmentation – The Thiomethoxymethyl Complexes [(bipy)M(CH2SCH3)]+ (M=Pt, Pd, Ni)

“…For decades, ion/molecule reactions (IMRs) of mass-selected ions A + and neutral molecules B conducted in the dilute gas phase constitute a powerful method to investigate the elementary steps of chemical reactions. [1][2][3][4][5][6][7][8][9][10][11][12][13] CÀ H-bond activation, [5,[14][15][16][17][18] oxygen-atom transfer, [19][20][21] and the concept two-state reactivity [22][23][24][25][26][27] are just a few out of many examples. While the operational details of IMRs vary for different experimental setups (e. g. triple-quadrupole mass spectrometers, [28][29][30] ICR mass spectrometers, [31][32][33][34][35] quadrupole ion-traps [28,[36][37][38][39][40][41][42] ), the general sequence of steps starts with the encounter of the ion A + and the neutral molecule B to form a charged adduct complex AB + (Figure 1).…”

Effects of Charge Transfer on the Adsorption of CO on Small Molybdenum‐Doped Platinum Clusters

“…[12][13][14][15] The good control over the cluster size, composition and charge state allows to distinguish the effects of these parameters on the studied reactions. Moreover, the highvacuum conditions of a gas-phase experiment eliminate the contaminating agents that could affect the reaction mechanism.…”

“…Small clusters in the gas phase have proven to be ideal model systems for investigating the fundamental aspects of complex reactions . The good control over cluster size, composition, and charge state allows the effects of these parameters on the studied reactions to be distinguished.…”

“…In particular, for n = 14 ν CO is redshifted upon Mo doping (see Figure 4-a). This suggests that the CO binding Pt site in MoPt 13 + is less positively charged than that in Pt 14 + and indicates an electron transfer from Mo to Pt. This was also seen in DFT calculations on the larger Pt 19 + CO and MoPt 18 + CO clusters.…”