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/sup 77/Se NMR. Application of J/sub Se-Se/ to the analysis of dialkyl polyselenides

Journal Article · · J. Am. Chem. Soc.; (United States)
DOI:https://doi.org/10.1021/ja00268a001· OSTI ID:5455164
; ;
Elemental selenium is partially reduced via either disproportionation or reaction with sodium methanolate and hydrazine in dipolar aprotic media. These reductions both give polyselenide ions with a known average chain length, Se/sub n//sup 2 -/(3less than or equal to n less than or equal to 7). Alkylation of these anions proceeds with loss of selenium and formation of a mixture of dialkyl polyselenides, R-Se/sub m/-R, with an average chain length m approx. 2.25-2.50. /sup 77/Se chemical shifts and /sup 1/H-/sup 77/Se and /sup 77/Se-/sup 77/Se coupling constants were measured for various dialkyl polyselenide mixtures. By observation of the selenium satellites in the /sup 77/Se NMR spectra the existence in the mixture of di-, tri-, tetra-, and pentaselenides was proved and the structure of the higher polyselenides established as linear chains. /sup 77/Se-/sup 80/Se isotope effects on the /sup 77/Se chemical shifts were measured and used for assignment of the homonuclear /sup 77/Se coupling constants. The /sup 77/Se chemical shifts of selenides show a large temperature variation. It is shown that such a large variation coupled with sample spinning can give rise to artificial signal splitting in proton noise decoupled NMR spectra.
Research Organization:
Univ. of Copenhagen, Denmark
OSTI ID:
5455164
Journal Information:
J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 108:8; ISSN JACSA
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400302* -- Organic Chemistry-- Isotope Effects-- (-1987)
CHALCOGENIDES
CHEMICAL SHIFT
COUPLING
COUPLING CONSTANTS
DATA
EVEN-ODD NUCLEI
EXPERIMENTAL DATA
INFORMATION
INTERMEDIATE COUPLING
INTERMEDIATE MASS NUCLEI
ISOMERIC TRANSITION ISOTOPES
ISOTOPE EFFECTS
ISOTOPES
J-J COUPLING
MAGNETIC RESONANCE
NMR SPECTRA
NUCLEAR MAGNETIC RESONANCE
NUCLEI
NUMERICAL DATA
ORGANIC COMPOUNDS
RADIOISOTOPES
RESONANCE
SECONDS LIVING RADIOISOTOPES
SELENIDES
SELENIUM 77
SELENIUM COMPOUNDS
SELENIUM ISOTOPES
SPECTRA
STABLE ISOTOPES
STRUCTURAL CHEMICAL ANALYSIS
TEMPERATURE DEPENDENCE