Amalgam electrodes: Direct electrochemical generation of cadmium macrocyclic complexes

Boudon, Corinne; Gisselbrecht, Jean Paul; Gross, Maurice

doi:10.1002/elan.1140040106

Cited by 3 publications

(1 citation statement)

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“…There is considerable interest in the development of electrochemical sensors for Cd(II) and other heavy metals, and several reports have appeared in the literature describing the use of several of the thiacrown ligands here as ionophores in ion-selective electrodes for cadmium. [27][28][29] In particular, electrochemical measurements employing [12]aneS 4 implied the formation a 2 : 1 ligand/Cd complex. 30 Our structural results now confirm that assignment.…”

Section: X-ray Structures Of Cd(ii) Complexesmentioning

confidence: 99%

Cadmium-113 NMR studies on homoleptic complexes containing thioether ligands: the crystal structures of [Cd([12]aneS4)2](ClO4)2, [Cd([18]aneS4N2)](PF6)2 and [Cd([9]aneS3)2](PF6)2

et al. 2006

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We report the measurement of 113Cd NMR chemical shift data for homoleptic thioether and related aza and mixed aza/thiacrown complexes. In a series of Cd(II) complexes containing trithioether to hexathioether ligands, we observe solution 113Cd NMR chemical shifts in the range of 225 to 731 ppm. Upfield chemical shifts in these NMR spectra are seen whenever: (a) the number of thioether sulfur donors in the complex is decreased, (b) a thioether sulfur donor is replaced by a secondary nitrogen donor, or (c) the size of the macrocycle ring increases without a change in the nature or number of the donor atoms. Changes in the identity of non-coordinating anions such as perchlorate or hexafluorophosphate have little effect upon the 113Cd NMR chemical shift in solution. We report the X-ray structure of the complex [Cd([12]aneS4)2](ClO4)2 ([12]aneS4 = 1,4,7,10-tetrathiacyclododecane) (1) which shows the first example of octakis(thioether) coordination of a metal ion, forming an unusual eight-coordinate square antiprismatic structure. We report the X-ray structure of the complex [Cd([9]aneS3)2](PF6)2 ([9]aneS3 = 1,4,7-trithiacyclononane) (3a) which shows hexakis(thioether) coordination to form a distorted octahedral structure. We have also prepared and characterized the Cd(II) complex of a mixed azathiacrown, [Cd([18]aneS4N2)](PF6)2 ([18]aneS4N2 = 1,4,10,13-tetrathia-7,16-diazacyclooctadecane) (6). Its X-ray structure shows a distorted octahedral S4N2 environment around the Cd(II) with the ligand coordinated in the rac fashion. We observe a solvent- and temperature-dependent 14N-1H coupling in the 1H NMR spectrum of the complex which is not present in analogous complexes with this ligand.

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Section: X-ray Structures Of Cd(ii) Complexesmentioning

confidence: 99%

Cadmium-113 NMR studies on homoleptic complexes containing thioether ligands: the crystal structures of [Cd([12]aneS4)2](ClO4)2, [Cd([18]aneS4N2)](PF6)2 and [Cd([9]aneS3)2](PF6)2

et al. 2006

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Electrochemistry of Cadmium

Stroka

Maksymiuk

Galus

2006

Encyclopedia of Electrochemistry

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The sections in this article are Double‐layer Properties of Cadmium Electrodes Electrochemical Properties and Kinetics of the Cd ( II )/ Cd ( Hg ) Systems Electrochemistry in Aqueous Solutions Kinetics of Simple Ions Influence of a Catalyst Influence of Inhibitors Electrochemistry in Mixed and Nonaqueous Solvents Electrochemical Properties of the Cadmium Complexes Determination of Stability Constants Electrochemical Preparation of Cadmium Complexes Preparation and Electrochemical Properties of Cadmium Chalcogenides CdS CdSe Cd Te Properties of Cadmium Intermetallic Compounds Cadmium Underpotential Deposition and Electrodeposition on Solid Electrodes Deposition of Cd on Cadmium Electrode Electrodeposition of Cd on Other Solid Substrates Gold Platinum Silver Copper Silicon Other Substrates Passivation and Corrosion of Cadmium Passivation of Cadmium Electrode Corrosion of Cadmium Applied Electrochemistry Batteries Cadmium–Mercuric Oxide Primary Cells Cadmium–Nickel Oxide ( Ni – Cd ) Secondary Cells Cadmium–Silver Oxide Secondary Cells Application in Electrochemical Sensors Potentiometric Sensors Amperometric‐voltammetric Sensors

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Complexation of macrocyclic ligands with relatively non-solvated metal ions generated in dichloromethane by electrochemical oxidation of amalgam electrodes

Bobrowski

Bond

Ellis³

1999

Inorganica Chimica Acta

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Amalgam electrodes: Direct electrochemical generation of cadmium macrocyclic complexes

Cited by 3 publications

References 34 publications

Cadmium-113 NMR studies on homoleptic complexes containing thioether ligands: the crystal structures of [Cd([12]aneS4)2](ClO4)2, [Cd([18]aneS4N2)](PF6)2 and [Cd([9]aneS3)2](PF6)2

Cadmium-113 NMR studies on homoleptic complexes containing thioether ligands: the crystal structures of [Cd([12]aneS4)2](ClO4)2, [Cd([18]aneS4N2)](PF6)2 and [Cd([9]aneS3)2](PF6)2

Electrochemistry of Cadmium

Complexation of macrocyclic ligands with relatively non-solvated metal ions generated in dichloromethane by electrochemical oxidation of amalgam electrodes

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