Thio derivatives of β-Diketones and their metal chelates. XV. Mass spectra of cobalt(III) and rhodium(III) chelates of some fluorinated Monothio-β-diketones

1974 ◽  
Vol 27 (6) ◽  
pp. 1177 ◽  
Author(s):  
M Das ◽  
SE Livingstone
Keyword(s):  
Thermal Degradation ◽  
Mass Spectrometer ◽  
Mass Spectra ◽  
Cobalt Complexes ◽  
Metal Chelates ◽  
Complex Ions ◽  
Molecular Ion ◽  
Derivatives Of ◽  
Bivalent State ◽  
Cobalt Chelates

The mass spectra of the cobalt(111) and rhodium(111) chelates of the fluorinated monothio-β-diketones RC(SH)=CHCOCF3 (R = Ph, p-MeC6H4, p-BrC6H4, p-FC6H4, and 2-thienyl) and of the cobalt(111) chelate of CH3C(SH)=CHCOCF3 have been obtained. The cobalt chelates do not give a peak for the molecular ion because of thermal degradation to the cobalt(11) complex CO(RCS=CHCOCF3)2, which then undergoes reactions in the mass spectrometer. Fluorine migration occurs with cobalt but not with rhodium. The cobalt complexes give rise to more metal-containing fragments than their rhodium analogues. Mechanisms are proposed for the reactions involving the metal-containing fragments. Cobalt undergoes valency changes to give cobalt(11) and cobalt(1) complex ions, whereas rhodium undergoes a valency change to the bivalent state only.

Thio derivatives of β-Diketones and their metal chelates. XVII. Mass spectra of iron(III) and ruthenium(III) chelates of some fluorinated Monothio-β-diketones

1974 ◽  
Vol 27 (10) ◽  
pp. 2115 ◽  
Author(s):  
M Das ◽  
SE Livingstone
Keyword(s):  
Thermal Degradation ◽  
Mass Spectrometer ◽  
Mass Spectra ◽  
Metal Chelates ◽  
Iron Chelates ◽  
Molecular Ion ◽  
Derivatives Of

The mass spectra of the iron(111) and rhodium(111) chelates of the fluorinated monothio-β-diketones RC(SH)=CHCOCF3 (R = Ph,p-MeC6H4, 2-thienyl) have been obtained. Whereas the ruthenium(111) chelates give a peak for the molecular ion, the iron(111) chelates do not, due to thermal degradation to the iron(11) complex Fe(RCS=CHCOCF3)2 which then undergoes reactions in the mass spectrometer. Fluorine migration occurs with two of the iron chelates but not with the ruthenium chelates. Mechanisms are proposed for the reactions of the ruthenium chelates.

Thio derivatives of β-diketones and their metal chelates. XVIII. Mass spectra of some metal chelates of the monothio derivatives of benzoylacetone anddibenzoylmethane

1975 ◽  
Vol 28 (3) ◽  
pp. 513 ◽  
Author(s):  
M Das ◽  
SE Livingstone
Keyword(s):  
Thermal Degradation ◽  
Mass Spectrometer ◽  
Mass Spectra ◽  
Zinc Complex ◽  
Free Ligand ◽  
Cobalt Complexes ◽  
Metal Chelates ◽  
Bivalent Metal ◽  
Free Ions ◽  
Derivatives Of

The mass spectra of the iron(III), cobalt(III), nickel(II) and zinc(II) complexes of the monothio-β-diketones RC(SH)=CHCOPh (R = Me, Ph) have been obtained. The iron and cobalt complexes of 3-mercapto-1-phenylbut- 2-en-1-one (R = Me) do not give a peak for the molecular ion due to thermal degradation to the bivalent metal complex Met(MeCS=CHCOPh)2 (Met = Fe, Co), which then undergoes reactions similar to those undergone by the nickel and zinc complexes. The most interesting feature of the spectra is the loss of hydrogen sulphide which does not occur with the free ligand or with metal complexes of fluorinated monothio-8-diketones RC(SH)=CHCOCF3. ��� The zinc complex of 3-mercapto-1,3-diphenylprop-2-en-1-one (R = Ph) undergoes fragmentation in the mass spectrometer to produce inter alia [ZnC6H5]+. However, the iron(III), cobalt(III), nickel(II) and palladium(II) complexes undergo thermal degradation in the mass spectrometer but the mass spectra of these four complexes give metal-free ions with m/e greater than m/e for L, due to fragmentation of the ion 2L.

Thio derivatives of b-diketones and their metal chelates. XIII. Mass spectra of zinc and nickel chelates of some fluorinated monothio-b-diketones

1974 ◽  
Vol 27 (1) ◽  
pp. 53 ◽  
Author(s):  
M Das ◽  
SE Livingstone
Keyword(s):  
Metal Ion ◽  
Mass Spectra ◽  
Metal Chelates ◽  
Cyclic Structure ◽  
Molecular Ion ◽  
Metal Free ◽  
Strong Peak ◽  
Nickel Chelates ◽  
Valence Change ◽  
Derivatives Of

The mass spectra of the zinc(11) and nickel(11) chelates of four fluorinated monothio-β-diketones, RC(SH)=CHCOCF3 (R = Ph, p-MeC6H4, 2-thienyl, Me), have been obtained. The mass spectra of the nickel chelates have considerably more peaks due to metal-containing species than the spectra of the zinc chelates, while the reverse is true for the metal-free fragments. All the zinc chelates give peaks for M (molecular ion), M ? CF3, M - L (LH = monothio-β-diketone), M - L ? CF2, LH, L, L - F, RCSCH and RCS. All the nickel chelates give peaks for M, M - F, M ? CF3, M - COCF3, M - L, M- 2L and L. In addition, some of the metal chelates give other peaks. Mechanisms are proposed for the reactions giving rise to some of these species. All the zinc and nickel chelates give a strong peak due to L+ arising from a valence change of the metal ion from the bivalent to the univalent state as follows: [Me11L2]+ → L+ + Me1L (Me = Zn, Ni). It is suggested that the ion L+ has a resonance-stabilized cyclic structure.

Thio derivatives of β-diketones and their metal chelates. XIX. Metal chelates of two new fluorinated Monothio-β-diketones and their mass spectra

1975 ◽  
Vol 28 (6) ◽  
pp. 1249 ◽  
Author(s):  
SE Livingstone ◽  
N Saha
Keyword(s):  
Mass Spectra ◽  
Metal Chelates ◽  
The Novel ◽  
Copper Chelates ◽  
Derivatives Of

The nickel(II), palladium(II), platinum(II), copper(II), zinc(II) and rhodium(III) chelates of the new fluorinated monothio-β-diketones RC(SH)=CHCOCF3 (R = Pri, Bui) and the iron(III), ruthenium(III) and cobalt(III) chelates of PriC(SH)=CHCOCF3 have been prepared. The mass spectra of all but the two copper chelates have been obtained. The novel features of the spectra are the occurrence of the ions M-(R-H), M-R, and M-LH and the loss of H2S from the ions M-LH and M-L.

The Mass Spectra of Imidoyl Halides and Bromoiminium Bromides

1973 ◽  
Vol 51 (1) ◽  
pp. 132-138 ◽  
Author(s):  
J. Gal ◽  
B. A. Phillips ◽  
R. Smith
Keyword(s):  
Mass Spectrometer ◽  
Alkyl Group ◽  
Mass Spectra ◽  
Halogen Atom ◽  
Fragmentation Pattern ◽  
Inlet System ◽  
Molecular Ion ◽  
Major Process ◽  
Hydrogen Rearrangement

The mass spectra of imidoyl halides 1–6 and bromoiminium bromides 7–9 have been studied and their fragmentation pattern discussed. Loss of halogen atom from the molecular ion of imidoyl halides to form a N-alkylnitrilium ion is a major process. When the N-alkyl group is larger than methyl the fragmentation of N-alkylnitrilium ions with hydrogen rearrangement to give the [PhC≡NH]+ ion becomes important. Thermolysis of bromoiminium bromides in the inlet system of the mass spectrometer produces imidoyl bromides via dealkylation (or dehydrobromination) and α,α-dibromobenzylamines via addition of bromide to the C=N bond.

The mass spectra of trifluoroacetyl-2,5-diketopiperazines. I. cyclo-(-Gly-X), cyclo-(-Ala-X) (X = Gly, Val, Leu, Ile), and cyclo-(-Ala-Ala)

1979 ◽  
Vol 57 (15) ◽  
pp. 2037-2051 ◽  
Author(s):  
George P. Slater ◽  
Lawrence R. Hogge
Keyword(s):  
Mass Spectrum ◽  
Mass Spectra ◽  
High Resolution Data ◽  
Fragmentation Pathways ◽  
Molecular Ion ◽  
Metastable Ions ◽  
Fragmentation Patterns ◽  
The Individual ◽  
Derivatives Of ◽  
Resolution Data

The trifluoroacetyl derivatives of the 2,5-diketopiperazines cyclo-(-Gly-X), cyclo-(-Ala-X) (X = Gly, Val, Leu, Ile), and cyclo-(-Ala-Ala) were examined by GC–MS. The molecular ion was readily detectable only for TFA-cyclo-(-Gly-Gly) (m/e 306, 9%). For those compounds containing a valyl or leucyl/isoleucyl residue the ion of highest mass in the spectrum was formed by elimination of C3H6 or C4H8, respectively, from the molecular ion. In the TFA-cyclo-(-Gly-X) series this ion corresponded to the molecular ion of TFA-cyclo-(Gly-Gly) (m/e 306), and in the TFA-cyclo-(-Ala-X) series, to the molecular ion of TFA-cyclo-(-Ala-Gly) (m/e 320). The fragmentation patterns proposed for these compounds are based on the further degradation of these parent ions so that each compound within a series has a similar mass spectrum. However, sufficient differences were detectable in the various spectra to permit identification of the individual DKP's.Many of the fragmentation pathways devised to explain the mass spectra were supported by high resolution data and appropriate metastable ions.

Thio derivatives of β-diketones and their metal chelates. XXI. Mass spectra of 1,1,1-Trifluoro-4-mercapto-4-(2'-naphthyl)but-3-en-2-one and its metal chelates

1976 ◽  
Vol 29 (2) ◽  
pp. 283 ◽  
Author(s):  
SE Livingstone ◽  
DS Moore
Keyword(s):  
Mass Spectrum ◽  
Mass Spectra ◽  
Metal Chelates ◽  
Fragmentation Pattern ◽  
Derivatives Of

The new monothio-β-diketone l,l,l-trifluoro-4-mercapto-4-(2'-naphthyl)but-3-en-2-one, βC10H7- C(SH)=CHCOCF3, and its chelates with iron(111), ruthenium(111), cobalt(111), rhodium(111, nickel(11), palladium(11), platinum(11) and zinc(11) have been prepared. The mass spectrum of the monothio-β-diketone displays considerably more peaks than that of its parent β-diketone. Both spectra give peaks for the ion CllH7+ (RC+ ; R = β-C10H7). The mass spectra of the metal chelates show some differences determined by the metal. All the metal chelates except that of zinc show peaks due to the ion M'-MetS and its daughter ions (M' = M for MetL2 and M - L for MetL3 ; L = β-C10H7C(S)=CHCOCF3). It is considered that the β-naphthyl group affects the fragmentation pattern, since the mass spectra differ considerably from those of metal chelates of other monothio-β-diketones.

The mass spectra of Schiff bases. I. Simple fissions and rearrangements

1966 ◽  
Vol 19 (2) ◽  
pp. 251 ◽  
Author(s):  
DJ Elias ◽  
RG Gillis
Keyword(s):  
Double Bond ◽  
Electron Impact ◽  
Schiff Bases ◽  
Mass Spectra ◽  
Hydrogen Transfer ◽  
Molecular Ion ◽  
Ring Carbon ◽  
Carbon Bonds ◽  
Ring Nitrogen ◽  
Derivatives Of

Under electron impact, Schiff bases give a stable molecular ion which undergoes simple fission at the ring-nitrogen and ring-carbon bonds. Ortho substitution leads to ions derived from five-membered heterocycles. Derivatives of o-methoxy-benzaldehyde exhibit a two-hydrogen transfer with fission of the azomethine double bond to give the amine radical-ion.

Thio derivatives of β-diketones and their metal chelates. XIV. Mass spectra of palladium and platinum chelates of some fluorinated Monothio-β-diketones

1974 ◽  
Vol 27 (4) ◽  
pp. 749 ◽  
Author(s):  
M Das ◽  
SE Livingstone
Keyword(s):  
Mass Spectra ◽  
Metal Chelates ◽  
Fragmentation Pattern ◽  
Derivatives Of ◽  
Zinc Nickel

The mass spectra of the palladium(11) and platinum(11) chelates of the fluorinated monothio-β- diketones, RC(SH)=CHCOCF3 (R = Ph, p-MeC6H4, p-BrC6H4, p-NO2C6H4, 2-thienyl), and of the palladium chelate of CH3C(SH)=CHCOCF3 have been obtained. The platinum chelates give rise to more metal-containing peaks than the palladium chelates. Mechanisms are proposed for the reactions involving the metal-containing fragments. A comparison of the mass spectra of the zinc, nickel, palladium and platinum chelates of these fluorinated monothio-β-diketones reveals that the fragmentation pattern is determined by the metal.

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.

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