Fourier transform mass spectrometric studies of isovalent rare earth ions Sc+, Y+ and Lu+ with methanol. Formation of dimethoxide—metal species M(OCH3)+2

Quantum Chemical Studies on Dioxygen Activation and Methane Hydroxylation by Diiron and Dicopper Species as well as Related Metal–Oxo Species

“…The reverse reaction of the reduction of methanol to methane is energetically favorable and it is actually observed to occur under ion-cyclotron-resonance conditions. 98 The electronic features and reactivities of TiO + and VO + are similar to those of ScO + because the partially filled nonbonding 1δ set has no direct effect on the metal oxygen bonds while the three bonding orbitals are fully occupied. These early MO + complexes have a very strong triple bond, and accordingly the reactivity of these complexes toward alkanes is low.…”

“…85 In contrast, the early MO + complexes (ScO + , TiO + , and VO + ) exhibit no reactivity toward alkanes and alkenes, due to their strong metaloxo bonds. Interestingly, Sc + reacts with methanol to yield ScO + and methane in the gas phase, 98 which is precisely the reverse reaction of methane hydroxylation.…”

Gas-phase transuranium chemistry: reactions of actinide ions with alcohols and thiols

“…In particular, the relative amounts of residual, unreacted M C can be compared to assess the overall reactivities, and it is clear that U C and Np C exhibited significantly greater net reactivities than did Pu C , Am C , Tb C and Tm C ; no clear reactivity differences within these two groups of M C could be definitively established. Based upon results for Ln C reacting with alcohols, 22,23,25 it is expected that oxophilic An C such as U C and Np C -the U-O and Np-O bond dissociation energies (D°) are >700 kJ mol 1 45 -should react with alcohols to produce AnO C , which may have been a dominant product not distinguishable from directly ablated AnO C . Referring to Fig.…”

“…21 Gas-phase reactions of lanthanide ions, Ln C , with alcohols have produced oxides, hydroxides, alkoxides, aryloxides, aldehydes and dehydrogenation complexes. 22 -25 The reaction pathways of the various Ln C can be interpreted in the context of electronic configurations and ionization potentials, and the ultimately produced products, such as Ln(OCH 3 2 C , typically reflect the high oxophilicity and distinct propensity of most lanthanides to exist in a trivalent state. Alkoxides are of particular interest with respect to condensed-phase chemistry and several thorium and uranium alkoxide and aryloxide compounds have been prepared.…”

Gas-phase reactions of atomic lanthanide cations with methyl chloride — Periodicities in reactivity

“…A plethora of investigations into lanthanide ion chemistry followed, in part to further characterize this requirement, but also motivated by general interests in the gas-phase and solution chemistry of lanthanides (2). Reactions of Ln + cations now have been investigated systematically with various inorganic and organic molecules, including hydrogen (3), oxygen (4), nitrous oxide (4), alkanes and cycloalkanes, alkenes (1,5,6), alcohol (7)(8)(9), benzene and substituted benzenes (10,11), phenol (12), orthoformates (10,13), ferrocene, and iron pentacarbonyl (14). Generally these studies show that the reactivity of Ln + varies along the 4f series often in a manner that appears to be determined by the accessibility, through electron promotion, of excited electronic configurations of the Ln + cations with two unpaired non-f electrons.…”