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000011775 0247_ $$2DOI$$a10.1016/j.ijms.2010.02.012
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000011775 041__ $$aeng
000011775 082__ $$a530
000011775 084__ $$2WoS$$aPhysics, Atomic, Molecular & Chemical
000011775 084__ $$2WoS$$aSpectroscopy
000011775 1001_ $$0P:(DE-Juel1)VDB78760$$aWallace, W.E.$$b0$$uFZJ
000011775 245__ $$aReactive MALDI mass spectrometry of saturated hydrocarbons: A theoretical study
000011775 260__ $$a[S.l.]$$bElsevier Science$$c2010
000011775 300__ $$a
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000011775 440_0 $$02787$$aInternational Journal of Mass Spectrometry$$v292$$x1387-3806$$y1
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000011775 520__ $$aRecently it has been shown that the cobaltocenium cation, prepared by the laser ablation of a CoCp(CO)(2)/fullerene matrix, may react with alkanes and polyethylenes in the gas phase via a dehydrogenation reaction to produce [Co(Cp)(2)(alkadiene)](+) ions without chain scission (W.E. Wallace, Chem. Commun. 2007, 4525-4527). To better understand these experimental observations, density functional calculations were used to obtain the gas phase binding energies and molecular structures of cobaltocenium, Co(Cp)(2)(+), with 1,3-butadiene, 2,4-hexadiene, and 2,3-hexadiene. Calculations were conducted for both cis and trans molecular configurations, in both singlet and triplet electronic states, and with a variety of cyclopentadienyl hapticities. For 1,3-butadiene the 18-electron rule would predict a [Co(eta(5)-Cp)(2)(1,3-butadiene)](+), however, the lowest energy structure, [Co(eta(5)-Cp)(2)(1,3-butadiene)](+), has a higher than expected cyclopentadienyl hapticity. In this structure a distance of nearly 0.5 nm between the metal core and the butadiene ligand leads to very little electron sharing. Thus the detected ions are better described as non-covalent ion-molecule complexes. In turn, the lack of orbital overlap leads to a low enthalpy giving the cis-butadiene complex a -13.0 kJ/mol binding energy and the trans-butadiene binding a -3.8 kJ/mol binding energy. These low binding energies lead to low levels of charged alkanes in the reactive ion formation process in agreement with experimental observations. Published by Elsevier B.V.
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000011775 65320 $$2Author$$aAlkane
000011775 65320 $$2Author$$aCobaltocene
000011775 65320 $$2Author$$aDehydrogenation
000011775 65320 $$2Author$$aDensity functional theory
000011775 65320 $$2Author$$aNon-covalent
000011775 65320 $$2Author$$aPolymer
000011775 7001_ $$0P:(DE-Juel1)129496$$aLewandowski, H.$$b1$$uFZJ
000011775 7001_ $$0P:(DE-Juel1)VDB78003$$aMeier, R.J.$$b2$$uFZJ
000011775 773__ $$0PERI:(DE-600)1484635-4$$a10.1016/j.ijms.2010.02.012$$gVol. 292$$q292$$tInternational journal of mass spectrometry$$v292$$x1387-3806$$y2010
000011775 8567_ $$uhttp://dx.doi.org/10.1016/j.ijms.2010.02.012
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