Thio derivatives of β-diketones and their metal chelates. VIII. Adducts of metal chelates of fluorinated monothio-β-diketones

1968 ◽  
Vol 21 (1) ◽  
pp. 103 ◽  
Author(s):  
RKY Ho ◽  
SE Livingstone ◽  
TN Lockyer
Keyword(s):  
Molecular Weight ◽  
Metal Complexes ◽  
Infrared Spectra ◽  
Metal Chelates ◽  
Spectral Measurements ◽  
Nitrobenzene Solution ◽  
Nickel Zinc ◽  
Derivatives Of ◽  
Infrared Data ◽  
Palladium Platinum

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.

Thio derivatives of β-diketones and their metal chelates. VI. Metal chelates of 3-Mercapto-1,3-diphenylprop-2-en-1-one and their infrared spectra

1967 ◽  
Vol 20 (6) ◽  
pp. 1065 ◽  
Author(s):  
SHH Chaton ◽  
SE Livingstone
Keyword(s):  
Metal Complexes ◽  
Infrared Spectra ◽  
Metal Ion ◽  
Free Ligand ◽  
Carbonyl Oxygen ◽  
Metal Chelates ◽  
The Other ◽  
Methyl Derivative ◽  
Derivatives Of

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).

Thio derivatives of β-diketones and their metal chelates. II. α-Substituted Monothio-β-diketones as ligands

1965 ◽  
Vol 18 (12) ◽  
pp. 1927 ◽  
Author(s):  
RKY Ho ◽  
SE Livingstone ◽  
TN Lockyer
Keyword(s):  
Carbon Atom ◽  
Metal Complexes ◽  
Infrared Spectra ◽  
Steric Hindrance ◽  
Metal Chelates ◽  
Methyl Group ◽  
Central Carbon Atom ◽  
Complexing Ability ◽  
Central Carbon ◽  
Derivatives Of

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).

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
Keyword(s):  
Carbonyl Group ◽  
Infrared Spectra ◽  
Nitrogen Heterocycles ◽  
Metal Chelates ◽  
Derivatives Of

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.

Organobismuth compounds. I. Studies on triphenylbismuth(V) derivatives, Ph3BiX2

1970 ◽  
Vol 48 (16) ◽  
pp. 2488-2493 ◽  
Author(s):  
R. G. Goel ◽  
H. S. Prasad
Keyword(s):  
Molecular Weight ◽  
Infrared Spectra ◽  
Molecular Species ◽  
Structural Features ◽  
Molecular Weights ◽  
Electrical Conductances ◽  
Conductance Data ◽  
Chemical Constitution ◽  
Derivatives Of ◽  
Coordinate Structures

Triphenylbismuth(V) acid derivatives of the type, Ph3BiX2, where X = halide, nitrate, cyanate, acetate, haloacetate, or cyanoacetate have been prepared. Infrared spectra (4000 to 200 cm−1 region), electrical conductances, and molecular weights of these compounds have been studied to elucidate their structural features and chemical constitution. The molecular weight and conductance data show that these compounds behave as molecular species in benzene or nitromethane. The infrared spectroscopic results also indicate non-ionic five-coordinate structures. Bi—X stretching frequencies have been assigned for the difluoride, dichloride, dinitrate, dicyanate, and diacetate. These frequencies occur in the region 410–240 cm−1.

Thio derivatives of β-diketones and their metal chelates. IX. Nickel and copper complexes of some new fluorinated monothio-β-diketones

1968 ◽  
Vol 21 (7) ◽  
pp. 1781 ◽  
Author(s):  
RKY Ho ◽  
SE Livingstone
Keyword(s):  
General Formula ◽  
High Spin ◽  
Copper Complexes ◽  
Nickel Complexes ◽  
Metal Chelates ◽  
Sulphur Atom ◽  
Derivatives Of ◽  
Infrared Data

Four new fluorinated monothio-β-diketones of general formula RC(SH)=CH- COCF3 have been prepared; they are: l,l,l-trifluoro-4-mercapto-4-(4-methylphenyl)but-3-en-2-one (R = p-methylphenyl), 1,1,1-trifluoro-4-mercapto-4- (4-methoxyphenyl)but-3-en-2-one (R = p-methoxyphenyl), 4-(4-bromophenyl)-l,l,l- trifluoro-4-mercaptobut-3-en-2-one (R = p-bromophenyl), and l,l,l-trifluoro-4- (2-furyl)-4-mercaptobut-3-en-2-one (R = 2-furyl). Their nickel complexes, which are brown and diamagnetic, yield stable high-spin bis-pyridine adducts. When R = p-MeC6H4, p-MeOC6H4, or p-BrC6H4 the ligand yields both copper(1) and copper(11) complexes but when R = 2-furyl only a copper(11) complex is obtained. Infrared data indicate that in the copper(1) complexes the ligand is coordinated through the sulphur atom only.

COORDINATION COMPLEXES OF TITANIUM (IV) HALIDES: III. PREPARATION AND INFRARED SPECTRA OF THE COMPLEXES OF TITANIUM TETRACHLORIDE WITH UREA, THIOUREA, AND SOME OF THEIR DERIVATIVES

1962 ◽  
Vol 40 (12) ◽  
pp. 2234-2242 ◽  
Author(s):  
Roland Rivest
Keyword(s):  
Molecular Weight ◽  
Oxygen Atom ◽  
Infrared Spectra ◽  
Titanium Tetrachloride ◽  
Coordination Complexes ◽  
Dinuclear Complexes ◽  
Derivatives Of

The following coordination complexes of titanium (IV) have been prepared: TiCl4•2CO(NH2)2, TiCl4•CO(NHCH3)2, TiCl4•2CO(NHCH3)2, 2TiCl4•2NH2CON(C6H5)2, 2TiCl4•2CO(NHC6H5)2 TiCl4•2CS(NH2)2, 2TiCl4•CS(NHC2H5)2, 2TiCl4•NH2CSN(C6H5)2, and 2TiCl4•CS(NHC6H5)2; their infrared spectra have been measured and their molecular weight determined. For urea and its derivatives the coordination to titanium (IV) is always through the oxygen atom. The phenyl derivatives of urea led to dinuclear complexes which were best explained by assuming halogen bridging between the titanium atoms. Thiourea and its derivatives gave complexes in which coordination occurred through one of the nitrogens in the case of thiourea and through both nitrogens in the case of the derivatives. Halogen bridging was again assumed to explain the formation of the dinuclear complexes.

Thio derivatives of β-diketones and their metal chelates. I. Some Monothio-β-diketones and their nickel(II) chelates

1965 ◽  
Vol 18 (5) ◽  
pp. 673 ◽  
Author(s):  
SHH Chaston ◽  
SE Livingstone ◽  
TN Lockyer ◽  
VA Pickles ◽  
JS Shannon
Keyword(s):  
Low Temperature ◽  
Metal Complexes ◽  
Infrared Spectra ◽  
Hydrogen Sulphide ◽  
Mass Spectrometric ◽  
Dilute Solution ◽  
Nickel Chelates ◽  
Derivatives Of ◽  
Diethyl Dithiophosphate ◽  
Yellow Compound

Monothio-β-diketones of general formula RC(SH)=CHCOR? (R = Me, R* = Me, Ph, OEt; R = Ph, R' = Ph, OEt; R = α-thienyl, R' = CF3; and 12 = R' = CMe,) have been prepared in order to study their metal complexes. Five of these thio derivatives are new and were prepared by treatment of a dilute solution of the corresponding β-diketone in alcohol with hydrogen sulphide at low temperature. Mass spectrometric examination has established the structures of MeC(SH)=CHCOPh and RC(SH)=CHCOCF, (R = α-thienyl). The red compounds PhC(SH)=CHCOPh (VI) and MeC(SH)=CHCOPh (V) can be oxidized to yellow products. The structure of the yellow compound (XV) obtained from (VI) was established by mass and n.m.r. spectroscopy as the disulphide PhCOCH=C(Ph)SSC(Ph)=CHCOPh. The molecular ion of (XV) undergoes novel rearrangement reactions involving, inter alia, elimination of H2S to produce a thiophene ion. The nickel chelates Ni(RCS=CHCOR')2 are brown, diamagnetic, and soluble in organic solvents. Unstable paramagnetic bis-pyridine adducts, derived from two of the nickel chelates, were isolated. The infrared spectra of the monothio-β-diketones and their nickel chelates are reported. The spectra of the monothio-β-diketones show no SH band at c. 2570 cm-1 ; this indicates strong chelation of the thiol hydrogen between the sulphur and oxygen atoms. The monothio-β-diketones display four characteristic bands which are assigned as follows : 1670-1590 cm-1, v(C--O) ; 1638-1530 cm-1, v(C=C) ; 1267-1190 cm-1, v(C=S) ; 837-805 cm-1, provisionally assigned as v(C=S) + δ(C-H). The nickel chelates exhibit five characteristic bands: 1590-1535 cm-1, V(C=C); 1542-1477 cm-1, v(C-0); 1261-1220 cm-1, v(C--S); 817-800 cm-1, provisionally assigned to v(C-S)+ δ(C-H); 499-451 cm-1, v(Ni-O). No band corresponding to v(Ni-S) was detected above 250 cm-1. However, the metal-sulphur stretching frequency was observed as a peak of medium intensity within the range 360-308 cm-1 in the spectra of bis(o-methylthiobenzenethiolo)-nickel(II) and the diethyl dithiophosphate complexes of nicke1(II), palladium(II), chromium(III), and cobalt(III).

Europium and cerium extraction by the nitrobenzene solution of dicarbolide in the presence of polyethylene glycols

1986 ◽  
Vol 51 (3) ◽  
pp. 498-515 ◽  
Author(s):  
Emanuel Makrlík ◽  
Petr Vaňura
Keyword(s):  
Molecular Weight ◽  
Polyethylene Glycol ◽  
Organic Phase ◽  
Perchloric Acid ◽  
Equilibrium Constants ◽  
Polyethylene Glycols ◽  
Individual Species ◽  
Nitrobenzene Solution ◽  
Separation Factors ◽  
Equilibrium Data

Extraction of Eu3+ and Ce3+ microamounts from 0.1-0.4M perchloric acid by the nitrobenzene solution of dicarbolide H+[Co(C2B9H11)2]- in the presence of polyethylene glycols (Mr = 200, 300, 400) has been studied. The equilibrium data and the typical maxima on the dependence of the metal distribution ratio on the total analytical concentration of polyethylene glycol in the system can be explained assuming that the species ML3+org, ML3+2org, ML3+3org, MLH2+-1org, and HL+org (where M3+ = Eu3+, Ce3+; L = polyethylene glycol) are extracted into the organic phase. The values of extraction and equilibrium constants in the organic phase were determined and the effect of the polyethylene glycol molecular weight on the equilibrium constants and on the abundances of individual species in the organic phase is discussed. It has been found that the addition of polyethylene glycol to the acid - nitrobezene - dicarbolide system increases the values of the separation factors αCe/Eu.

Sign in / Sign up

Export Citation Format

Share Document