Journal article
Activation of aromatic rings by early transition metal ions in the gas phase. Implications for the metal-catalyzed [2 + 2 + 2] cycloaddition of alkynes and nitriles
Organic Mass Spectrometry, Vol.28(12), pp.1616-1622
12/1993
DOI: 10.1002/oms.1210281238
Abstract
The reactions of a series of monocyclic and bicyclic arenes with early transition metal ions (Sc+, Y+, Nb+ and Ta+) and their oxides and dioxides were studied in a Fourier transform ion cyclotron resonance mass spectrometer. Ring cleavage of the nitrogen-containing heterocycles results in loss of HCN as the dominant pathway. Thermochemical considerations, secondary reactions and correlations with solution cyclotrimerization reactions indicate that the MC4H4+ product is a metallacyclopentadiene. Based on correspondence between the reactivities of a series of early metals with their valence electron counts, the reactivities of quinoline and isoquinoline and the decomposition behavior of the products, a metallacycloheptatriene intermediate is proposed for the heteroaromatic ring cleavage reaction. These results are compared to metal complexes in solution which catalyze the [2 + 2 + 2] cyclotrimerization of alkynes and nitriles.
Details
- Title: Subtitle
- Activation of aromatic rings by early transition metal ions in the gas phase. Implications for the metal-catalyzed [2 + 2 + 2] cycloaddition of alkynes and nitriles
- Creators
- R. Marshall Pope - University of ArizonaSteven W. Buckner - University of Arizona
- Resource Type
- Journal article
- Publication Details
- Organic Mass Spectrometry, Vol.28(12), pp.1616-1622
- Publisher
- John Wiley & Sons, Ltd
- DOI
- 10.1002/oms.1210281238
- ISSN
- 0030-493X
- eISSN
- 1096-9888
- Number of pages
- 7
- Language
- English
- Date published
- 12/1993
- Academic Unit
- Medicine Administration
- Record Identifier
- 9984627325202771
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