NOVEL ELECTRON IMPACT-INDUCED HYDROGEN REARRANGEMENTS IN THE MASS-SPECTRA OF ORGANORHENIUM HYDRIDES AND ALKYLS
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abstract
The electron impact-induced hydrogen rearrangement of an organorhenium hydride is described, in which the remote hydrogen is identified to be the hydride hydrogen by deuterium-labelling experiments. Rearrangement accompanies intra-ligand cleavage of the triphenylphosphine ligand, an unusual event in itself, resulting in neutral loss of benzene from the molecular ion. Closer examination of the electron impact mass spectra of a series of organorhenium alkyl compounds indicates that another rearrangement of a beta hydrogen from the alkyl ligand onto the metal center produces the rhenium hydride, which then undergoes rearrangement and neutral loss. These two rearrangements serve to explain the heretofore anomalous fragment peaks in the spectra of the organorhenium alkyl compounds. 1986 Elsevier Science Publishers B.V.