Siloxanes are a significant impurity in syngas feedstocks and an important source of silicon in combustion synthesis applications. However, little is known regarding the fundamental combustion chemistry of siloxane compounds. The impact of two organic silicon species with different but related chemical structures, trimethylsilanol (TMSO) and hexamethyldisiloxane (HMDSO), on syngas auto-ignition behavior was investigated in this study using physical and computational experiments. A rapid compression facility (RCF) was used to create temperatures of 1010-1070 K and pressures of 8-10.3 atm for autoignition experiments. Experiments with trace concentrations of TMSO (100 ppm, mole basis) or HMDSO (100 ppm) were added to a surrogate syngas blend (CO and H-2 with a molar ratio of 2.34:1, air levels of dilution, with molar equivalence ratios of phi = 0.1). The measured ignition delay times showed both siloxane species promote ignition behavior with TMSO yielding faster ignition delay times by approximately 37% and HMDSO yielding faster times by approximately 50% compared with the reference syngas mixture which contained no siloxanes. A computational study was conducted to interpret the results of the ignition experiments. Because detailed chemistry does not exist for these organo-silicon compounds, the effects of the addition of CH3, H, and OH radicals to H-2 and CO mixtures were explored to simulate the potential rapid decomposition of the siloxanes in the H-2 and CO system. Addition of the radicals decreased the predicted ignition delay times when compared with the H-2 and CO mixture simulations without the radical species, but the simulations did not fully capture the behavior observed in the experiments, indicating the siloxane chemistry is more complex than providing a rapid source of radicals. (C) 2019 The Combustion Institute. Published by Elsevier Inc. All rights reserved.