Molybdenum Oxide Cluster Ions in the Gas Phase: Reactions with Small Alcohols
Full article
| Общее |
Language:
Английский,
Genre:
Full article,
Status:
Published,
Source type:
Original
|
| Journal |
Organometallics
ISSN: 0276-7333
, E-ISSN: 1520-6041
|
| Output data |
Year: 1998,
Volume: 17,
Number: 1,
Pages: 25-31
Pages count
: 7
DOI:
10.1021/OM9704253
|
| Authors |
Fialko Elena F.
1
,
Kikhtenko Andrey V.
1
,
Goncharov Vladimir B.
1
|
| Affiliations |
| 1 |
Boreskov Institute of Catalysis, Pr. Akademika Lavrentieva 5, 630090 Novosibirsk, Russia
|
|
Funding (2)
|
1
|
International Science Foundation
|
RBG 000
|
|
2
|
International Science Foundation
|
RBG 300
|
The gas-phase reactions of molybdenum oxide cluster ions MoxOy+ (x = 1−3, y = 1−9) with small alcohols have been investigated using Fourier transform ion cyclotron resonance mass spectrometry. The product branch ratios are reported. The reactions of MoxOy+ with alcohols can be envisioned as proceeding via metal insertion into C−H and C−O bonds. C−H bond insertion leads to alcohol dehydrogenation and aldehyde elimination, whereas insertion into the C−O bonds results in alcohol dehydration and formation of metal−alkyl groups. Moreover, an increase of the chain length and branching lead to C−C bond cleavage. The most intriguing process is the reaction of the Mo3O9+ ion with more than one CH3OH molecule yielding Mo3O9(C2H5)+ and Mo3O9(C3H7)+ ions. The Mo3O9CH3+ ion was found to be the key intermediate of the polymerization process. Molybdenum oxides are protonated in the presence of alcohols. The upper and lower limits for the MoxOy proton affinities were estimated as PA(MoO) < 180 kcal/mol, PA(Mo2O4, Mo2O5, Mo3O8) = 188 ± 8 kcal/mol, PA(MoO2) = 202 ± 5 kcal/mol, PA(MoO3, Mo2O6, Mo3O9) > 207 kcal/mol.