The gas phase pyrolysis of trimethylstibine and triethylstibine has been studied by infrared laser powered homogeneous pyrolysis. The role of free radicals in both homogeneous and surface decomposition was investigated by matrix isolation electron spin resonance (ESR) spectroscopy. For trimethylstibine, the major process at low pressures is methyl radical loss and subsequent abstraction of hydrogen from the starting material. For triethylstibine, the major process in decomposition on heated quartz surfaces is ethyl radical loss, whereas the gas phase studies suggest a significant molecular elimination route. For both compounds, material deposited from the gas phase is essentially pure antimony, indicating that homogeneous reactions play little part in carbon incorporation.
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