Fragmentation and rearrangement processes in the mass spectra of perfluoroaromatic compounds. Part XI. Heterocyclic derivatives of phosphorus and some transition metals

1979 ◽  
Vol 57 (3) ◽  
pp. 335-341 ◽  
Author(s):  
Timothy R. B. Jones ◽  
Jack M. Miller ◽  
Sylvia A. Gardner ◽  
Marvin D. Rausch

The mass spectra of a number of phospholes and metalloles of general structure 1 and 2 are[Formula: see text]discussed with respect to their fragmentation and ion rearrangement processes. Of special interest is the migration of ring fluorines to the central atom during fragmentation. The bonding principles involved for the postulated intermediates are discussed.

1969 ◽  
Vol 47 (10) ◽  
pp. 1613-1620 ◽  
Author(s):  
J. M. Miller

The mass spectra of compounds of the type (C6F5)4M (M = Si, Ge, Sn, and Pb) have been studied. Bond forming rearrangements were detected, involving fluorine abstraction by the central atom, forming perfluorophenylene ions and neutral metal fluoride species. The heavier metals give simpler spectra and fragmentation schemes. The bulk of the ion current is carried by fluorocarbon ions for the silicon derivative and by organometallic or metal fluoride ions in the other three cases, SnF+ and PbF+ forming the base peaks in their spectra. When M is carbon in the compounds (C6F5)3COH and (C6F5)2CO, there is little evidence for rearrangements and transfer of fluorine to the central carbon atom.


1973 ◽  
Vol 51 (12) ◽  
pp. 1945-1951 ◽  
Author(s):  
G. F. Lanthier ◽  
J. M. Miller ◽  
A. J. Oliver

The mass spectra of R3MSC6F5 and R3MOC6F5 (R = CH3 or C6H5; M = Si, Ge, Sn) are reported and compared with the corresponding pentafluorophenyl derivatives. The sulfur and oxygen compounds show fewer rearrangements leading to the formation of metal fluorides than do simple C6F5 derivatives. The ions R3M+ are usually observed as the base peaks. Ions containing Sn—S appear more stable than Sn—O species, while the reverse seems true for silicon.


1976 ◽  
Vol 54 (9) ◽  
pp. 1478-1486 ◽  
Author(s):  
Timothy R. B. Jones ◽  
Jack M. Miller ◽  
J. Lowell Peterson ◽  
Devon W. Meek

A comprehensive low-resolution study of the mass spectra of the compounds C6F5M(CH3)2, where M = N, P, As, is described, fragmentation pathways being assigned with the aid of normal metastable ions and mass analyzed ion kinetic energy spectra (mikes). A comparison of these spectra has re-affirmed the absence of halogen transfer processes for atoms such as N which are incapable of providing the necessary vacant orbitals apparently prerequisite in the mechanisms. The influence of increased coordination to phosphorus and effects on halogen transfer processes are discussed with respect to the mass spectra of the compounds C6F5PX(CH3)2, X = O, S, Se and the gold adducts C6F5P(CH3)2•AuX, X = Cl, Br, I.


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