Fragmentation and rearrangement processes in the mass spectra of perhalogenoaromatic compounds. Part II. Pentafluorophenyl derivatives of GroupIV

1969 ◽  
Vol 47 (10) ◽  
pp. 1613-1620 ◽  
Author(s):  
J. M. Miller
Keyword(s):  
Mass Spectra ◽  
Central Atom ◽  
Metal Fluoride ◽  
Fluoride Ions ◽  
Bond Forming ◽  
Central Carbon ◽  
Type C ◽  
Derivatives Of ◽  
Rearrangement Processes ◽  
Neutral Metal

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.

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
Keyword(s):  
Transition Metals ◽  
Special Interest ◽  
Mass Spectra ◽  
Central Atom ◽  
General Structure ◽  
Heterocyclic Derivatives ◽  
Derivatives Of ◽  
Rearrangement Processes

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.

Mass Spectra of Organometallic Compounds. IV. Some Mononuclear Fluorocarbon Derivatives of Transition Metals

1969 ◽  
Vol 23 (2) ◽  
pp. 137-147 ◽  
Author(s):  
R. B. King
Keyword(s):  
Transition Metals ◽  
Mass Spectrometer ◽  
Mass Spectra ◽  
Organometallic Compounds ◽  
Metal Fluoride ◽  
Derivatives Of ◽  
Neutral Metal

The mass spectra of the following fluorocarbon derivatives of transition metals have been investigated: (a) the perfluoroalkyl derivatives RfMo (CO)3C5H5 ( Rf = CF3 and C3F7); (b) the perfluoroacyl derivatives CF3COM(CO)3C6H5 (M = Mo and W), C3F7COM(CO)3C5H5 (M = Mo and W), and C3F7COFe(CO)2C6H6; (c) the perfluoraryl derivatives RfFe(CO)2C5H5 ( Rf/ = C6F5, p-HC6F4, 3, 4-H2C6F3, and p-CF3C6F4); (d) the hexafluorobutyne derivatives [(CF3)2C]3 MNCCH3 (M = Mo and W); and (e) the bis (trifluoromethyl)tetramethylbicyclo-[2.2,2] octatriene complexes C14H14F6Fe (CO)3 and C5H5CoC14H14F6. Unusual features observed in these mass spectra include the following: (a) Evidence for elimination of the neutral metal fluoride fragments FeF2 and C5H5CoF; (b) evidence for the elimination of neutral HF and CF2 fragments; (c) evidence for the elimination of a bridge in the bicyclo [2,2,2] octatriene derivatives; (d) decarbonylation of RfCOMo (CO)3C5H5 compounds, but not their tungsten analogs, in the mass spectrometer; and (e) evidence for the eliminations of C4F4 and CH3CN fragments in the mass spectra of the [(CF3)2C2]3MNCCH3 complexes.

Fragmentation and Rearrangement Processes in the Mass Spectra of Perhalogenoaromatic Compounds. Part IX. Pentafluorophenol and Pentafluorothiophenol Derivatives of Group IV

1973 ◽  
Vol 51 (12) ◽  
pp. 1945-1951 ◽  
Author(s):  
G. F. Lanthier ◽  
J. M. Miller ◽  
A. J. Oliver
Keyword(s):  
Mass Spectra ◽  
Group Iv ◽  
Metal Fluorides ◽  
Derivatives Of ◽  
Rearrangement Processes

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.

Studies in Negative-Ion Mass Spectrometry. XII. Electron Attachment to a Series of Bis(1,1,1,5,5,5-hexafluoropentane-2,4-dionato)-metal Complexes

1979 ◽  
Vol 32 (11) ◽  
pp. 2405 ◽  
Author(s):  
DR Dakternieks ◽  
IW Fraser ◽  
JL Garnett ◽  
IK Gregor
Keyword(s):  
Mass Spectra ◽  
Electron Attachment ◽  
Negative Ions ◽  
Fragmentation Pathway ◽  
Negative Ion ◽  
Metal Fluoride ◽  
Class A ◽  
Negative Ion Mass Spectrometry ◽  
Fragment Ions ◽  
Rearrangement Processes

Results of electron-attachment reactions in the gas phase as well as negative-ion mass spectra are given for a series of bis(1,1,1,5,5,5-hexafluoropentane-2,4-dionato)metal(1) complexes, (ML2), with the divalent metals MgII, MnII, Co11, Nil1, Cu11 and ZnII. While molecular, [ML2]- or [ML2]-, and ligand, [L]-, ions are present in the negative-ion mass spectra, the lability of the ligand C-F and C-CF3 bonds enables rearrangement processes involving fluorine atom transfers to become significant in the decompositions of both molecular and fragment ions, particularly for the class (a) metals, for which significant yields of [MLF2] and [MLF] negative ions were obtained. Thus, the predominant fragmentation pathway for such metal-containing complexes, for which metastable peaks have been assigned, occurs in the sequence [ML2]- -(*) → (MLF2]- - (8) → [L]- or alternatively [ML2]- -(*) → (MLF2]- - (8) → [L]- with the latter fragmentation in these sequences involving the elimination of the divalent metal fluoride, MF2.

Fragmentation and rearrangement processes in the mass spectra of perhalogenoaromatic compounds. Part X. Pentafluorophenyl dimethyl derivatives of group V

1976 ◽  
Vol 54 (9) ◽  
pp. 1478-1486 ◽  
Author(s):  
Timothy R. B. Jones ◽  
Jack M. Miller ◽  
J. Lowell Peterson ◽  
Devon W. Meek
Keyword(s):  
Mass Spectra ◽  
Energy Spectra ◽  
Group V ◽  
Fragmentation Pathways ◽  
Transfer Processes ◽  
Metastable Ions ◽  
Ion Kinetic Energy ◽  
Derivatives Of ◽  
Rearrangement Processes ◽  
Resolution Study

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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