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).

Hydrogen sulphide – halogen complexes studied by matrix isolation vibrational spectroscopy

1985 ◽  
Vol 63 (7) ◽  
pp. 1705-1707 ◽  
Author(s):  
U. P. Agarwal ◽  
A. J. Barnes ◽  
W. J. Orville-Thomas
Keyword(s):  
Low Temperature ◽  
Vibrational Spectroscopy ◽  
Infrared Spectra ◽  
Hydrogen Sulphide ◽  
Matrix Isolation ◽  
Reaction Products ◽  
Hydrogen Halides ◽  
Stretching Vibration

Infrared spectra are reported of mixtures of hydrogen sulphide with chlorine or bromine in low-temperature argon or nitrogen matrices. The H2S … Cl2 and H2S … Br2 complexes were identified from the perturbed halogen stretching vibration. Absorptions due to the corresponding hydrogen halides provided evidence that reaction was occurring between the hydrogen sulphide and halogen (despite the use of a twin-jet deposition), and other reaction products were tentatively identified from the observed absorptions.

scholarly journals Copper(II) derivatives of the stereochemically adaptive ligands 1,2-bis(2′-pyridyl)ethane and bis(2-pyridyl)disulfide

1970 ◽  
Vol 48 (20) ◽  
pp. 3185-3192 ◽  
Author(s):  
M. Keeton ◽  
A. B. P. Lever ◽  
B. S. Ramaswamy
Keyword(s):  
Low Temperature ◽  
Vibrational Spectroscopy ◽  
Infrared Spectra ◽  
Metal Ion ◽  
Structural Types ◽  
Distorted Octahedral ◽  
Derivatives Of

Tetrahedral, square, square pyramidal, and tetragonally distorted octahedral complexes of copper(II) with the title ligands are characterized by electronic and vibrational spectroscopy (at ambient and low temperature) and magnetism. The infrared spectra are utilized to infer information about the conformation of the ligands in these complexes. The variation in structural types observed is believed to be a consequence of the stereochemical adaptability of these ligands to the electronic demands of the metal ion.

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. 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. 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).

scholarly journals Functionalised Terpyridines and Their Metal Complexes—Solid-State Interactions

Chemistry ◽  
2021 ◽  
Vol 3 (1) ◽  
pp. 199-227
Author(s):  
Young Hoon Lee ◽  
Jee Young Kim ◽  
Sotaro Kusumoto ◽  
Hitomi Ohmagari ◽  
Miki Hasegawa ◽  
...  
Keyword(s):  
Solid State ◽  
Metal Complexes ◽  
Crystal Structures ◽  
Weak Interactions ◽  
Dispersion Interactions ◽  
Derivatives Of

Analysis of the weak interactions within the crystal structures of 33 complexes of various 4′-aromatic derivatives of 2,2′:6′,2″-terpyridine (tpy) shows that interactions that exceed dispersion are dominated, as expected, by cation⋯anion contacts but are associated with both ligand–ligand and ligand–solvent contacts, sometimes multicentred, in generally complicated arrays, probably largely determined by dispersion interactions between stacked aromatic units. With V(V) as the coordinating cation, there is evidence that the polarisation of the ligand results in an interaction exceeding dispersion at a carbon bound to nitrogen with oxygen or fluorine, an interaction unseen in the structures of M(II) (M = Fe, Co, Ni, Cu, Zn, Ru and Cd) complexes, except when 1,2,3-trimethoxyphenyl substituents are present in the 4′-tpy.

scholarly journals The Exchange of Cyclometalated Ligands

Molecules ◽  
2021 ◽  
Vol 26 (1) ◽  
pp. 210
Author(s):  
Alexander D. Ryabov
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Bond Activation ◽  
Bond Cleavage ◽  
Cyclopalladated Complexes ◽  
Derivatives Of ◽  
Cyclometalated Ligand ◽  
Incoming Ligand

Reactions of cyclometalated compounds are numerous. This account is focused on one of such reactions, the exchange of cyclometalated ligands, a reaction between a cyclometalated compound and an incoming ligand that replaces a previously cyclometalated ligand to form a new metalacycle: + H-C*~Z ⇄ + H-C~Y. Originally discovered for PdII complexes with Y/Z = N, P, S, the exchange appeared to be a mechanistically challenging, simple, and convenient routine for the synthesis of cyclopalladated complexes. Over four decades it was expanded to cyclometalated derivatives of platinum, ruthenium, manganese, rhodium, and iridium. The exchange, which is also questionably referred to as transcyclometalation, offers attractive synthetic possibilities and assists in disclosing key mechanistic pathways associated with the C–H bond activation by transition metal complexes and C–M bond cleavage. Both synthetic and mechanistic aspects of the exchange are reviewed and discussed.

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