Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

sup 207 Pb NMR, mass spectrometric, and electrochemical studies on labile lead(II) dithiocarbamate complexes: Formation of mixed mercury-lead complexes at a mercury electrode in dichloromethane solution

Journal Article · · Inorganic Chemistry; (USA)
DOI:https://doi.org/10.1021/ic00335a043· OSTI ID:6730288
;  [1];  [2]
  1. Deakin Univ., Geelong, Victoria (Australia)
  2. Univ. of Melbourne, Parkville, Victoria (Australia)
+ Show Author Affiliations
{sup 207}Pb NMR spectra have been observed in dichloromethane for series of Pb(RR{prime}dtc){sub 2} compounds (RR{prime}dtc = dialkylthiocarbamate). The resonances are rather broad, and molecular weight determinations show that this is caused by polymerization reactions. Ligand exchange between different Pb(RR{prime}dtc){sub 2} compounds is fast on the NMR time scale, and the complexes are therefore labile. The labile nature of the Pb(RR{prime}dtc){sub 2} systems in the solid state is confirmed by mass spectrometric measurements on mixtures of different complexes. Electrochemical reduction of Pb(RR{prime}dtc){sub 2} in dichloromethane (0.1 M Bu{sub 4} NClO{sub 4}) at mercury electrodes takes place in a single reversible two-electron step to give lead amalgam and free (RR{prime}dtc){sup {minus}}, the reversibility of this process further confirming the lability of the complexes. At platinum electrodes, initially an irreversible reduction occurs to generate elemental lead and (RR{prime}dtc){sup {minus}}. However, long-term behavior at platinum electrodes is complicated by the gradual coating of the electrode with elemental lead, thereby generating a lead electrode at which reversible responses are observed. Electrochemical oxidation processes at mercury electrodes are best described in terms of oxidation of the electrode in the presence of Pb(RR{prime}dtc){sub 2}. The electrochemistry in solution and the nature of the isolated products in the solid state indicate that when mercury and lead are competing for dithiocarbamate in a ligand deficient situation, then mercury is the successful element. 13 refs., 5 figs., 4 tabs.
OSTI ID:
6730288
Journal Information:
Inorganic Chemistry; (USA), Journal Name: Inorganic Chemistry; (USA) Vol. 29:10; ISSN 0020-1669; ISSN INOCA
Country of Publication:
United States
Language:
English

Similar Records

Voltammetric, coulometric, mercury-199 NMR, and other studies characterizing new and unusual mercury complexes produced by electrochemical oxidation of mercury(II) diethyldithiocarbamate. Crystal and molecular structure of octakis(N,N-diethyldithiocarbamato)pentamercury(II) perchlorate
Journal Article · Tue Mar 31 23:00:00 EST 1987 · J. Am. Chem. Soc.; (United States) · OSTI ID:6367518
Multinuclear magnetic resonance (/sup 31/P, /sup 77/Se, /sup 199/Hg) and electrochemical studies of nonlabile mercury(II) complexes with group 15/group 16 donor ligands
Journal Article · Wed May 18 00:00:00 EDT 1988 · Inorg. Chem.; (United States) · OSTI ID:5833101
Generation of mercury and cadmium cationic complexes from oxidation processes observed in the presence of dimethylmercury and dimethylcadmium at mercury, platinum, and glass carbon electrodes
Journal Article · Mon Feb 29 23:00:00 EST 1988 · Organometallics; (United States) · OSTI ID:5099292

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400202 -- Isotope Effects
Isotope Exchange
& Isotope Separation
400500 -- Photochemistry
CARBAMATES
CARBONIC ACID DERIVATIVES
CARBOXYLIC ACID SALTS
CHEMISTRY
COMPLEXES
DATA
ELECTROCHEMISTRY
ELECTRODES
EVEN-ODD NUCLEI
EXPERIMENTAL DATA
HEAVY NUCLEI
INFORMATION
ISOMERIC TRANSITION ISOTOPES
ISOTOPES
LEAD 207
LEAD COMPLEXES
LEAD ISOTOPES
MASS SPECTRA
MERCURY COMPLEXES
NUCLEI
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
RADIOISOTOPES
SECONDS LIVING RADIOISOTOPES
SPECTRA
STABLE ISOTOPES
SULFUR COMPOUNDS