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.

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. 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.

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 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. 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.

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.

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