Solvation of O(2)(-) and O(4)(-) by p-difluorobenzene and p-xylene studied by photoelectron spectroscopy.

Anion photoelectron spectra of the O(2)(-) . arene and O(4)(-) . arene complexes with p-xylene and p-difluorobenzene are presented and analyzed with the aid of calculations on the anions and corresponding neutrals. Relative to the adiabatic electron affinity of O(2), the O(2)(-) . arene spectra are blueshifted by 0.75-1 eV. Solvation energy alone does not account for this shift, and it is proposed that a repulsive portion of the neutral potential energy surface is accessed in the detachment, resulting in dissociative photodetachment. O(2)(-) is found to interact more strongly with the p-difluorobenzene than the p-xylene. The binding motif involves the O(2)(-) in plane with the arene, interacting via electron donation along nearby C-H bonds. A peak found at 4.36(2) eV in the photoelectron spectrum of O(2)(-) . p-difluorobenzene (p-DFB) is tentatively attributed to the charge transfer state, O(2)(-) . p-DFB(+). Spectra of O(4)(-) . arene complexes show less blueshift in electron binding energy relative to the spectrum of bare O(4)(-), which itself undergoes dissociative photodetachment. The striking similarity between the profiles of the O(4)(-) . arene complexes with the O(4)(-) spectrum suggests that the O(4)(-) molecule remains intact upon complex formation, and delocalization of the charge across the O(4)(-) molecule results in similar structures for the anion and neutral complexes.

Reactions between CO and small molybdenum suboxide cluster anions.

Reaction products resulting from small molybdenum suboxide cluster anions and carbon monoxide were studied with both mass spectrometry and anion photoelectron (PE) spectroscopy. In addition to the C6O6- product proposed previously, a number of unsaturated carbonyls were identified as terminal products in these reactions. A new PE spectrum of what may be C6O6-, in which the contribution from the Fe(CO)4- contaminant is subtracted, is reported. Additionally, the PE spectra of Mo(CO)5-, MoO(CO)3-, and MoO2(CO)n- (n=1 and 2) are presented, along with a new PE spectrum of an additional contaminant, Ni(CO)3-. Evidence of photodissociation of MoO(CO)3- to MoO-+3 CO is observed in the PE spectrum of MoO(CO)3-.