The oxidation of dithiocarbamato complexes of nickel, copper and zinc

Brinkhoff, H. C.; Cras, J. A.; Steggerda, J. J.; Willemse, J.

doi:10.1002/recl.19690880602

Cited by 87 publications

(14 citation statements)

References 11 publications

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“…The observed C-N distances are n o t conclusive with respect to the increase o f the C-N bond order as indicated by infrared and nm r measurements. T he difference in the C-S distances agree w ith the infrared spectra (Brinkhoff et al, 1970). …”

Section: Description Of the Moleculesupporting

confidence: 73%

“…In preceding papers, the preparations and properties o f diiodo-N ,N ,N ',N '-tetrabutylthiuram disulphidem ercury(II) (Brinkhoff et al, 1969) and o f the analogous ethyl derivative (Brinkhoff et al 1970) were reported. T he proposed m olecular structure was confirmed by an X -ray analysis o f the analogous methyl derivative, H gI2(M e4tds).…”

Section: Introductionmentioning

confidence: 99%

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Crystal and molecular structure of diiodo-N,N,N?,N?-tetramethylthiuramdisulphidemercury(II)

Beurskens

Cras²,

Noordik³

et al. 1971

Journal of Crystal and Molecular Structure

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The crystal and m olecular structure o f diiodo-N jN .N '.N '-tetram ethylthiuram disulphidem ercuryQ I), H gI2(S2C N (C H 3)2)2, has been determ ined by a three-dimensional X -ray analysis. The com pound crystallizes in the m onoclinic space group P 2 i/c w ith the unit cell dimensions a = 7-957 ± 4 , b = 22-639 ± 7 , c = 9-956 ± 6 A and /} = 112-14 ± 5°;Z = 4. Intensities were obtained w ith an autom atic diffractometer. T he structural param eters were refined by least-squares m ethods to a conventional R factor o f 0-044 for 1294 non-zero observed reflexions. T he m ercury is in distorted tetrahedral coordination w ith two iodine and two sulphur atom s. The H g-I distances are 2.654 ± 2 and 2-661 ± 2 A; the Hg-S distances are 2-651 ± 7 and 2-882 ± 7 A. T he thiuram disulphide ligand consists o f two planar units S2C N C 2, nearly perpendicular to each other. B ond distances o f the ligand are com pared w ith distances in tetraalkylthiuram disulphide molecules an d agree w ith infrared observations.

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Section: Description Of the Moleculesupporting

confidence: 73%

Section: Introductionmentioning

confidence: 99%

Crystal and molecular structure of diiodo-N,N,N?,N?-tetramethylthiuramdisulphidemercury(II)

Beurskens

Cras²,

Noordik³

et al. 1971

Journal of Crystal and Molecular Structure

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“…Indeed addition of halogens results in ligand-centered oxidation to give tetrahedral thiuram disulfide complexes [ZnX 2 {R 2 CN(S)S-SC(S)NR 2 }] resulting from sulfur-sulfur bond formation (eqn. 16) [57]. The thiuram disulfide here is only weakly bound and can readily be displaced and thus could potentially be released in a biological system under oxidizing conditions.…”

Section: Current/amentioning

confidence: 96%

Metal-dithiocarbamate complexes: chemistry and biological activity

Hogarth¹

2012

MRMC

248

157

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Dithiocarbamates are highly versatile mono-anionic chelating ligands which form stable complexes with all the transition elements and also the majority of main group, lanthanide and actinide elements. They are easily prepared from primary or secondary amines and depending upon the nature of the cation can show good solubility in water or organic solvents. They are related to the thiuram disulfides by a one-electron redox process (followed by dimerisation via sulfur-sulfur bond formation) which is easily carried out upon addition of iodide or ferric salts. Dithiocarbamates are lipophilic and generally bind to metals in a symmetrical chelate fashion but examples of other coordination modes are known, the monodentate and anisobidentate modes being most prevalent. They are planar sterically non-demanding ligands which can be electronically tuned by judicious choice of substituents. They stabilize metals in a wide range of oxidation states, this being attributed to the existence of soft dithiocarbamate and hard thioureide resonance forms, the latter formally resulting from delocalization of the nitrogen lone pair onto the sulfurs, and consequently their complexes tend to have a rich electrochemistry. Tetraethyl thiuramdisulfide (disulfiram or antabuse) has been used as a drug since the 1950s but it is only recently that dithiocarbamate complexes have been explored within the medicinal domain. Over the past two decades anti-cancer activity has been noted for gold and copper complexes, technetium and copper complexes have been used in PET-imaging, dithiocarbamates have been used to treat acute cadmium poisoning and copper complexes also have been investigated as SOD inhibitors.

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“…In this group of bis(dtc) complexes only the copper compounds showed a reversible behaviour. This is reflected in a remarkable way in the preparative oxidation of dtc complexes, only the copper complex giving a reaction product of the same stoichiometry C u (dtc)2+, nickel [10], palladium and platinum[ll] giving tris-complexes, M (dtc)3+, with the metal in the oxidation state +4.…”

Section: Voltammetric Studymentioning

confidence: 99%

Metal complexes with two different sulfur containing ligands—II

Linden¹

1972

Journal of Inorganic and Nuclear Chemistry

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The synthesis and characterization of a series of mixed l,l-/l,2-dithiolene complexes, M [S2C2(CN)2] [SüCNR*]* with z = -1, M = Ni, Cu, Pd, Pt and with 2 = 0, M = Ni, Cu, Au, M [S2C2(CN)2] [S2C N C N ]2' , M = N i, Pd, and N i[S 2C2(CN)2] [S2COC2H5] -are reported. Voltammetric studies in dichloromethane revealed that the mixed complexes could be oxidized in a one electron step, the half-wavepotentials of which were generally in the middle between those for the unmixed complexes. The C-N stretching frequencies observed in the i.r. spectra of the M [S2C2(CN)2] [S2CNR2]2 complexes are reported. the 1,1-and 1,2-dithiolato ligand system s. N ick e l bis-com plexes w ith tw o different 1,2-dithiolato ligands w ere rep o rted [l], and the exchange reactions of th ese and related 1,2-dithiolenes w ere studied with voltam m etric techniques [1,2], *Part-I. Ref. [5]. 7. H. C. Brinkhoff, Ree. Trav. Chim. 90,377 (1971). 8. (a). P. T. Beurskens, J. A . Cras and J, J, Steggerda, Inorg. Chem, 7, 810 (1968); (b), H. C. IN T R O D U C T IO N T h ere is a growing interest in m etal com p lex es containing tw o different sulfur donor ligands, especially th o se w ithBrinkhoff, Thesis, Nijmegen, 1970. 9. J. G. M. van der Linden,R ec. Trav. Chim. 90,1027 (1971).

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The oxidation of dithiocarbamato complexes of nickel, copper and zinc

Cited by 87 publications

References 11 publications

Crystal and molecular structure of diiodo-N,N,N?,N?-tetramethylthiuramdisulphidemercury(II)

Crystal and molecular structure of diiodo-N,N,N?,N?-tetramethylthiuramdisulphidemercury(II)

Metal-dithiocarbamate complexes: chemistry and biological activity

Metal complexes with two different sulfur containing ligands—II

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