Thio derivatives of β-diketones and their metal chelates. XXIII. Adducts of nickel(II) chelates of fluorinated Monothio-β-diketones with nitrogen heterocycles

1976 ◽  
Vol 29 (6) ◽  
pp. 1209 ◽  
Author(s):  
SE Livingstone ◽  
JH Mayfield ◽  
DS Moore

Paramagnetic adducts of the nickel(11) chelates of the fluorinated monothio-β-diketones RC(SH)=CHCOCF3 (R = β-naphthyl, p-ClC6H4, m-ClC6H4, m-BrC6H4, m-MeC6H4, 3,4-Cl2C6H3) have been obtained with pyridine, y-picoline, 2,2'-bipyridyl, and 1,l0-phenanthroline. They are of the type NiL2(base)2 (L = RCS=CHCOCF3; base = py, γpic, �bpy, �phen). With 2,2',2"-terpyridyl two types of adduct were isolated: (a) mononuclear NiL2(trpy) and (b) trinuclear Ni3L6(trpy)2. The infrared spectra of all the adducts display v(C-O) in the range 1552-1580 cm-l; this band is characteristic of a bidentate monothio-β-diketonato ligand. The spectra of the mononuclear terpyridyl adducts display in addition a v(C=O) band at c. 1650 cm-1, indicating that one carbonyl group is not coordinated.

1967 ◽  
Vol 20 (6) ◽  
pp. 1065 ◽  
Author(s):  
SHH Chaton ◽  
SE Livingstone

Complexes of 3-mercapto-1,3-diphenylprop-2-en-1-one, PhC(SH)=CHCOPh, with iron(III), cobalt(III), rhodium(III), nickel(II), palladium(II), platinum(II), copper(II), silver(I), zinc(II), cadmium(II), and mercury(II) have been prepared and characterized. Complexes of 4- mercaptopent-3-en-2-one, MeC(SH)=CHCOMe, with cobalt(III) and cadmium(II) and of ethyl thioacetoacetate, MeC(SH)=CHCOOEt, with cobalt(III) and copper(I) are also reported. The infrared spectra of the complexes of 3-mercapto-1,3- diphenylprop-2-en-1-one are discussed. The similarity of the spectra of the silver(I), cadmium(II), and mercury(II) complexes to those of the free ligand and its S-methyl derivative, PhC(SMe)=CHCOPh, indicate that in these three complexes the carbonyl oxygen of the ligand is not, or is at most weakly, coordinated to the metal ion. The assignments of the principal bands in the other metal complexes of this ligand are: 1550- 1525 cm-1, v(C-C); 1480-1458 cm-1, v(C=O); 1438-1412 cm-1, v(C=O)+δ(C-H); 1270-1260 cm-1, v(C--S); 498-437 cm-1, v(M-O); 399-376 cm-1, v(M-S).


1968 ◽  
Vol 21 (1) ◽  
pp. 103 ◽  
Author(s):  
RKY Ho ◽  
SE Livingstone ◽  
TN Lockyer

Complexes of l,l,l-trifluoro-4-mercapto-4-phenylbut-3-en-2-one, PhC(SH)= CHCOCF3, with cobalt(111), nicke1(11), palladium(11), platinum(11), copper(11), zinc(11), cadmium(11), and mercury(11) have been prepared and characterized. Their infrared spectra and the spectra of metal complexes of two other fluorinated monothio-β-diketones are discussed. Adducts of nickel (11) palladium(11), platinum(11), zinc(11), cadmium(11), mercury(11), and lead(11) complexes of the fluorinated monothio-β-diketones, RC(SH)=CHCOCF3 (R = Ph, α-thienyl, or Me), with pyridine, α-picoline, γ-picoline, 2,2'-bipyridyl, 1,l0-phenanthroline, 2,9-dimethyl-1,l0-phenanthroline, 2,2',2"-terpyridyl, or triphenylphosphine are described. Molecular weight and visible spectral measurements on PdL2(PPh3)2 (L = C4H3SC(SH)=CHCOCF3) show that in nitro- benzene and toluene solution one phosphine moiety is lost. Similarly, ZnL2 pic2 (pic = α- or γ-picoline) loses one molecule of picoline in nitrobenzene solution. The infrared data indicate that in the adducts nickel, zinc, and probably cadmium are six-coordinate and palladium, platinum, mercury, and lead are four-coordinate, while zinc is five-coordinate in the mono-adducts ZnL2 pic.


1965 ◽  
Vol 18 (12) ◽  
pp. 1927 ◽  
Author(s):  
RKY Ho ◽  
SE Livingstone ◽  
TN Lockyer

The α-methyl substituted monothio-β-diketones, 4-mercapto-3-methylpent-3-en-2-one, MeC(SH)=C(Me)COMe, and 3-mercapto-2-methyl-1,3-diphenylprop-2-en-1-one, PhC(SH)=C(;Me)COPh, were prepared; the former was not obtained pure. The complexing ability of these ligands appears to be weaker than that of other monothio-β-diketones; this can be partly explained on the basis of steric hindrance caused by the methyl group attached to the central carbon atom. The diamagnetic complexes, Ni(MeCS=CMeCOMe)2, Co(MeCS=CMeCOMe)3, and Ni(PhCS=CMeCOPh)2 were obtained but attempts to prepare other metal complexes of these ligands were unsuccessful. The infrared spectra of the three metal chelates display four characteristic bands for which assignments are given: 1570-1540 cm-1, v(C--C); 1525-1500 cm-1, v(C-0); 1230-1223 cm-1, v(C--8); 497-458 cm-1, v(M-0).


1966 ◽  
Vol 20 (3) ◽  
pp. 159-160 ◽  
Author(s):  
T. S. Herman

The effects of chlorine atoms on the fundamental frequencies of the s-triazine ring are discussed and the vibrational assignments in the region 1600–700 cm−1 are extended. The variation in the position of the C3N3-ring bending mode in the region near 810 cm−1 is discussed.


Author(s):  
N. A. Slovokhotova ◽  
K. N. Anisimov ◽  
G. M. Kunitskaya ◽  
N. E. Kolobova

1952 ◽  
Vol 24 (4) ◽  
pp. 623-625 ◽  
Author(s):  
S. E. Wiberley ◽  
S. C. Bunce

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