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@ARTICLE{Wallace:11775,
author = {Wallace, W.E. and Lewandowski, H. and Meier, R.J.},
title = {{R}eactive {MALDI} mass spectrometry of saturated
hydrocarbons: {A} theoretical study},
journal = {International journal of mass spectrometry},
volume = {292},
issn = {1387-3806},
address = {[S.l.]},
publisher = {Elsevier Science},
reportid = {PreJuSER-11775},
year = {2010},
note = {Record converted from VDB: 12.11.2012},
abstract = {Recently it has been shown that the cobaltocenium cation,
prepared by the laser ablation of a CoCp(CO)(2)/fullerene
matrix, may react with alkanes and polyethylenes in the gas
phase via a dehydrogenation reaction to produce
[Co(Cp)(2)(alkadiene)](+) ions without chain scission (W.E.
Wallace, Chem. Commun. 2007, 4525-4527). To better
understand these experimental observations, density
functional calculations were used to obtain the gas phase
binding energies and molecular structures of cobaltocenium,
Co(Cp)(2)(+), with 1,3-butadiene, 2,4-hexadiene, and
2,3-hexadiene. Calculations were conducted for both cis and
trans molecular configurations, in both singlet and triplet
electronic states, and with a variety of cyclopentadienyl
hapticities. For 1,3-butadiene the 18-electron rule would
predict a [Co(eta(5)-Cp)(2)(1,3-butadiene)](+), however, the
lowest energy structure,
[Co(eta(5)-Cp)(2)(1,3-butadiene)](+), has a higher than
expected cyclopentadienyl hapticity. In this structure a
distance of nearly 0.5 nm between the metal core and the
butadiene ligand leads to very little electron sharing. Thus
the detected ions are better described as non-covalent
ion-molecule complexes. In turn, the lack of orbital overlap
leads to a low enthalpy giving the cis-butadiene complex a
-13.0 kJ/mol binding energy and the trans-butadiene binding
a -3.8 kJ/mol binding energy. These low binding energies
lead to low levels of charged alkanes in the reactive ion
formation process in agreement with experimental
observations. Published by Elsevier B.V.},
keywords = {J (WoSType)},
cin = {ICG-4},
ddc = {530},
cid = {I:(DE-Juel1)VDB793},
pnm = {Terrestrische Umwelt},
pid = {G:(DE-Juel1)FUEK407},
shelfmark = {Physics, Atomic, Molecular $\&$ Chemical / Spectroscopy},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000277854900005},
doi = {10.1016/j.ijms.2010.02.012},
url = {https://juser.fz-juelich.de/record/11775},
}