You could have a look at the semiconductor industry. The compounds used there are sometimes explosive (silanes), often toxic (hydrazine, varied organo-something, phosphine and many more), corrosive (fluoro-anything). People who use them are not always chemists as they need more skills. In production plants things go more routinely, in development people have to use more varied compounds in diverse environments.
What about launcher rockets? Spark- and friction- sensitive solid propellants. Hydrazine, Mmh, Udmh, nitrogen tetroxide in hundreds of tons. What limits the accidents is that people are very wary of the risks and safety measures are followed there. Makes for impressive videos on youtube.