Recent studies of the formation of arsane in the borohydride/arsenate reaction demonstrate the occurrence of condensation cascades whereby small quantities of di- and triarsanes are formed. In this study, the isotopic composition of these di- and triarsanes was examined using deuterium labelled borohydrides. A statistical model was employed to construct the mass spectra of all diarsane and triarsane isotopologues (As2H (n) D4-n and As3H (n) D5-n ) from the mass spectra of isotopically pure compounds (As2H4, As2D4, As3H5, and As3D5). Subsequent deconvolution of the experimental mixed spectra shows that incorporation of hydrogen closely follows the binomial distribution, in accord with arsane formation. The H/D distribution in arsane, diarsane, and triarsane isotopologues is binomial in the absence of any interference. However, this is significantly altered by the presence of some transition metals; presented here, for the first time, are the effects of Rh(iii). The presence of Rh(iii) in the As(iii)/[BD4](-) system entails the incorporation of hydrogen into the arsanes arising from the solvent, altering the expected binomial H/D distribution.
The Binomial Distribution of Hydrogen and Deuterium in Arsanes, Diarsanes, and Triarsanes Generated from As(III)/[BHn D4-n](-) and the Effect of Trace Amounts of Rh(III) Ions
D'Ulivo A;
2012
Abstract
Recent studies of the formation of arsane in the borohydride/arsenate reaction demonstrate the occurrence of condensation cascades whereby small quantities of di- and triarsanes are formed. In this study, the isotopic composition of these di- and triarsanes was examined using deuterium labelled borohydrides. A statistical model was employed to construct the mass spectra of all diarsane and triarsane isotopologues (As2H (n) D4-n and As3H (n) D5-n ) from the mass spectra of isotopically pure compounds (As2H4, As2D4, As3H5, and As3D5). Subsequent deconvolution of the experimental mixed spectra shows that incorporation of hydrogen closely follows the binomial distribution, in accord with arsane formation. The H/D distribution in arsane, diarsane, and triarsane isotopologues is binomial in the absence of any interference. However, this is significantly altered by the presence of some transition metals; presented here, for the first time, are the effects of Rh(iii). The presence of Rh(iii) in the As(iii)/[BD4](-) system entails the incorporation of hydrogen into the arsanes arising from the solvent, altering the expected binomial H/D distribution.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
