Journal
JOURNAL OF PHYSICAL CHEMISTRY A
Volume 117, Issue 6, Pages 1299-1309Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jp307418c
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Funding
- National Science Foundation [CHE-1049580]
- ACS
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1049580] Funding Source: National Science Foundation
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Metal-cyclopentadienyl bond dissociation energies (BDEs) were measured for seven metallocene ions (Cp2M+, Cp = eta(5)-cyclopentadienyl = c-C5H5, M = Ti, V, Cr, Mn, Fe, Co, Ni) using threshold collision-induced dissociation (TCID) performed in a guided ion beam tandem mass spectrometer. For all seven room temperature metallocene ions, the dominant dissociation pathway is simple Cp loss from the metal. Traces of other fragment ions were also detected, such as C10H10+, C10H8+ C8H8+, C3H3+, H2M+, C3H3M+, C6H6M+, and C7H6M+, depending on the metal center. Statistical modeling of the Cp-loss TCID experimental data, including consideration of energy distributions, multiple collisions, and kinetic shifts, allow the extraction of 0 K [CpM+- Cp] BDEs. These are found to be 4.85 +/- 0.15, 4.02 +/- 0.14, 4.22 +/- 0.13, 3.51 +/- 0.12, 4.26 +/- 0.15, 4.57 +/- 0.15, and 3.37 +/- 0.12 eV for Cp2Ti+, Cp2V+, Cp2Cr+, Cp2Mn+, Cp2Fe+, Cp2Co+, and Cp2Ni+, respectively. The measured BDE trend is largely in line with arguments based on a simple molecular orbital picture, with the exception of the anomalous case of titanocene, most likely attributable to its bent structure. The new results presented here are compared to previous literature values and are found to provide a more complete and accurate set of thermochemistry.
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