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Application of specific deuterium labeling and nuclear magnetic resonance spectroscopy to the study of the mechanism of pyrolysis of tert-butylarsine and tert-butylarsine-d sub 2

Journal Article · · Chemistry of Materials; (United States)
OSTI ID:5410753

The synthesis of tert-butylarsine-d{sub 2} from tert-butylarsenic dichloride and LiAlD{sub 4} is described. No resonances at 2.65 ppm (from AsH{sub 2}) are observed in the {sup 1}H NMR spectrum, indicating the isotopic purity is greater than 95%. The pyrolyses of tert-butylarsine and tert-butylarsine-d{sub 2} were studied by using a flow reactor operated between 425 and 550{degree}C at total pressures of 0.001, 5, and 700 Torr. At 5 and 700 Torr, nitrogen was used as the carrier gas. The volatile products of the reaction were trapped in a liquid nitrogen cooled trap, transferred under vacuum into an NMR tube, and quantitatively analyzed by using {sup 1}H NMR spectroscopy. Three important results from the study are (1) the isobutane produced during the pyrolysis of tert-butylarsine-d{sub 2} was Me{sub 3}CD, (2) C{sub 2}Me{sub 6} was proven not to be a product of the reaction, (3) isobutane was found to be the major product at atmospheric pressure, while isobutene was predominant at low pressures in agreement with previous studies.

OSTI ID:
5410753
Journal Information:
Chemistry of Materials; (United States), Journal Name: Chemistry of Materials; (United States) Vol. 2:5; ISSN CMATE; ISSN 0897-4756
Country of Publication:
United States
Language:
English