Gas-phase reactivity of alkenes toward methylmercury cation

Abstract

The gas-phase reactivity of the electrophilic methylmercury cation towards a series of alkenes has been determined by ion cyclotron resonance spectroscopy. The rate of mercurinium ion formation was established to increase with increasing methyl substitution on the double bond.

Correlation of Ionization Potentials and HOMO Energies versus Relative Reactivities of Cl2, of Br2, and of I2 with Representative Acyclic Alkenes. Comparison with Other Additions to Alkenes

“…The negative slope in each of the plots in Figure c,d indicates that the product has an increased amount of electron density in the π bond. One explanation for this phenomenon, which has been proposed in other systems, ,10b, is that back-bonding from the electrophile (here I 2 ) to the alkene could be absent in the adsorbed form B and present in the complex C.…”

Mass spectrometry of organomercurials

“…Among these studies, the search for condensed phase reaction intermediates was of special value. For example, mercurinium ions were the subject of investigations by Bach et al (6)(7)(8) and by the authors of this review (5,9,10). These aspects of the mass spectrometry of organomercury compounds will be discussed in the present work.…”

“…Various mass spectrometric methods were employed to generate these ions and to investigate their properties in the gas phase (6,7,9,10). These studies were started by Bach and coworkers, using ion-cyclotron resonance (6).…”

“…The demonstration of the possibility of the existence of mercurinium ions is one of the most interesting problems in the chemistry of the organomercury compounds (1 11). Various mass spectrometric methods were employed to generate these ions and to investigate their properties in the gas phase (6,7,9,10). These studies were started by Bach and coworkers, using ion-cyclotron resonance (6).…”

“…Among these studies, the search for condensed phase reaction intermediates was of special value. For example, mercurinium ions were the subject of investigations by Bach et al (6)(7)(8) and…”