Structural studies of metal dithiocarbamates. II. The crystal and molecular structure of copper diethyldithiocarbamate

Bonamico, M.; Dessy, G.; Mugnoli, Angelo; Vaciago, A.; Zambonelli, L.

doi:10.1107/s0365110x65004619

Cited by 231 publications

(70 citation statements)

References 8 publications

(10 reference statements)

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“…The slight shortening of S(1)-C(6) and S(4)-C(9) relative to the other two S-C bonds is possibly significant, and could be associated with the lengthening of the bonds from these sulphur atoms to zinc. In other respects the dimensions of the dimethyldithiocarbamate group are not significantly different from those in ZDMC itself (Klug, 1966) or those found in the dithiocarbamates of nickel (II), copper (II), and zinc (II) (Bonamico, Dessy, Mariani, Vaciago & Zambonelli, 1965;Bonamico, Dessy, Mugnoli, Vaciago & Zambonelli, 1965;Bonamico, Mazzone et aL, 1965).…”

Section: Description and Discussionmentioning

confidence: 68%

The structure of bis-(N,N-dimethyldithiocarbamato)pyridinezinc

Fraser¹,

Harding²

1967

Acta Cryst

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Section: Description and Discussionmentioning

confidence: 68%

The structure of bis-(N,N-dimethyldithiocarbamato)pyridinezinc

Fraser¹,

Harding²

1967

Acta Cryst

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“…The redox reaction of the p-TsCl and Cu(I) species results in a tolylsulfonyl radical that is capable of initiating MMA, forming a monomer radical and the corresponding Cu(II) catalyst. The bond length of CuOS, 0.230 nm, is greater than that of CuOCl, 0.210 nm, 23,24 and the greater the bond length, the weaker the bond energy. Therefore, the generated radical captures the S 2 CNEt 2 group preferentially because of the weaker bond energy of CuOS.…”

Section: Methodsmentioning

confidence: 92%

Living radical polymerization of methyl methacrylate catalyzed by cuprous N,N‐diethyldithiocarbamate

Qiu

2002

J. Polym. Sci. A Polym. Chem.

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“…The opposite is true at high k (11-12 A-1). The numerical results of these fits are summarized in Table 1. (21) to 2.32 A for dithiocarbamates (22). Molecular orbital studies (23,24) as well as electron paramagnetic resonance analysis (24) suggest appreciable ligand-to-metal -r-covalency in copper(II)bis(thiosemicarbazonato) complexes.…”

Section: Discussionmentioning

confidence: 99%

Characterization of the blue copper site in oxidized azurin by extended x-ray absorption fine structure: Determination of a short Cu—S distance

Tullius

Frank

Hodgson

1978

Proc. Natl. Acad. Sci. U.S.A.

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The primary coordination environment of the "blue" copper ion in oxidized azurin has been elucidated by x-ray absorption spectroscopy. The most striking-feature is the unambiguous presence of a very short copper-sulfur, distance at 2.10 + 0.02 A. Nitrogen ligands, presumed to be from imidazoles, are found at 1.97 A. There is some evidence that the copper coordination sphere may be completed by a second sulfur, the distance of which is determined with much less certainty.Proteins that contain the "blue" (or type 1) copper site (1) have long offered a challenge to chemists to explain their unique spectroscopic and redox properties. Some of the basic aspects of the structure of such blue sites have already become clear, as revealed by interpretation of several types of spectroscopic data. The model for the blue site of bean plastocyanin put forth by Gray and coworkers (2) is probably the best distillation of current spectroscopic and chemical information on blue copper. The ligand field spectrum implies a distorted tetrahedral coordination of the copper, which is also reasonable when the high redox potential of the copper is considered. A thiolate sulfur from cysteine is proposed as one of the metal ligands. Two imidazole nitrogens from histidines are also implicated as ligands, from NMR studies (3-5). The fourth ligand of copper is less certain. A deprotonated peptide nitrogen from the protein has been proposed as this ligand (6), but methionine sulfur now seems to be the most likely possibility. The x-ray protein structure of poplar plastocyanin has recently been solved to 2.7 A resolution (7). The copper in this plastocyanin is coordinated by cysteinate, two imidazoles, and methionine.The availability of even a high-resolution x-ray crystallographic structure of a blue protein would not necessarily explain all of the unusual spectroscopic and redox properties of blue copper. Subtle changes in bond distance and coordination geometry, which the limited accuracy of even a good protein crystal structure might render difficult to resolve, can be expected to have major effects on these properties.A technique that has been recently used to examine the environment of a selected element in a complex macromolecular system is x-ray absorption spectroscopy. The fine structure that occurs at energies above the x-ray absorption edge (called EXAFS) provides a way of determining distances, numbers, and h-ypes of ligands coordinating a metal. Since the EXAFS method does not require crystalline samples, it can be applied to the study of metalloproteins under noncrystalline or physiological conditions (8)(9)(10)(11). In contrast to macromolecular crystallographic results, where it is difficult to obtain high accuracy except in the few cases of very well refined structures, EXAFS can provide accurate metal-to-ligand distances (12). Coupled with the element-selective nature of the measurements, the EXAFS technique is ideal for investigating the environment of a specific metal ion in a protein.In order to further elucidate t...

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Structural studies of metal dithiocarbamates. II. The crystal and molecular structure of copper diethyldithiocarbamate

Cited by 231 publications

References 8 publications

The structure of bis-(N,N-dimethyldithiocarbamato)pyridinezinc

The structure of bis-(N,N-dimethyldithiocarbamato)pyridinezinc

Living radical polymerization of methyl methacrylate catalyzed by cuprous N,N‐diethyldithiocarbamate

Characterization of the blue copper site in oxidized azurin by extended x-ray absorption fine structure: Determination of a short Cu—S distance

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