EXPERIMENTAL AND THEORETICAL EVIDENCE FOR AS-H BOND-CLEAVAGE IN THE DECOMPOSITION OF PRIMARY ARYLARSINES

Decomposition of 2-CH3C6H4AsD2 in vacuo at 600-1000-degrees-C gives toluene, which is deuterated with 0, 1, 2, or 3 D atoms in the methyl group. Theoretical studies suggest that this distribution of D atoms can only occur if the primary process for decomposition of the primary arsine is As-D bond cleavage and if this is followed by reductive elimination to give As and toluene or by rearrangement of CH3C6H4AsD . to DHAsC6H4CH2., which then abstracts D from another 2-CH3C6H4AsD2 molecule.