The kinetics of the reactions SiH 3 + SiH 3 and SiH 3 + NO, SiH 3 + C 3H 6, C 3H 4, and C 2H 4 are examined with time-resolved IR diode laser spectroscopy. The use of SiH 3Br as a precursor for direct photochemical production of SiH 3 at 193 nm is demonstrated. SiH 3 is observed to react with NO ( k(NO) = (2.5 ± 0.5) × 10 −12 cm 3 molecule −1 s −1), C 3H 6 and C 3H 4 ( k(C 3H 6) = (2.4 ± 0.3) × 10 −13 and k(C 3H 4) ⩽ (1.8 ± 0.4) × 10 −14 cm 3 molecule −1 s −1) but is unreactive toward C 2H 4 ( k(C 2H 4) ⩽ (3 ± 3) × 10 −15 cm 3 molecule −1 s −1). An upper limit to the bimolecular rate constant for the radical recombination process, SiH 3 + SiH 3, is determined, k rc ⩽ (6.1 ± 3.5) × 10 −11 cm 3 molecule −1 s −1.