Abstract
The major mononuclear aluminum species obtained in the reaction of aluminum atoms with dimethyl sulfide (DMS) and diethyl sulfide (DES), under cryogenic conditions, are the C-S insertion products, CH3AlSCH3 and CH3CH2AlSCH2CH3, respectively, showing that aluminum atoms can activate C-S bonds. The magnetic parameters were extracted from the EPR spectrum. Support for the spectral assignment was obtained by repeating the experiments with 13C-labeled dimethyl sulfide yielding 13CH3AlS13CH3. DFT calculations using the M06 functional have proven to be effective in predicting the isotropic and anisotropic Al hyperfine interaction values of the aluminum atom C-S insertion products. In addition, the thioalkyl radicals, CH3SCH2• and CH3CH2SCH•CH3 were formed in the aluminum atom reaction.
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