MATRIX-ISOLATION STUDY OF THE REACTION OF (CH3)3AL WITH HYDROGEN-SULFIDE AND MERCAPTANS - SYNTHESIS AND SPECTRA OF MOLECULAR AL2S3

The high-temperature pyrolytic reaction of (CH3)3Al with H2S followed by trapping into argon matrices at 14 K has led to the formation and i solation of molecular Al2S3. Identification was made based on band pos itions, lack of deuterium shift, the observation of CH3D when D2S was employed, and a poor spectral match to known aluminum sulfides and by analogy to the molecular species B2O3 and Al2O3. The spectra are sugge stive of a V-shaped molecule, also similar to B2O3 and in contrast to the linear structure of Al2O3. Local density functional calculations w ere also carried out in support of the experimental work. Reaction of (CH3)3Al with methyl and ethyl mercaptan led to the formation of (CH3) 2AlSR (R = CH3, C2H5), probably in the known dimeric structure.