In Lucky Starr and the Rings of Saturn, a novel unrelated to the Robot series but featuring robots programmed with the Three Laws, John Bigman Jones is almost killed by a Sirian robot on orders of its master.
Asimov's Three Law robots (or Asenion) can experience irreversible mental collapse if they are forced into situations where they cannot obey the First Law, or if they discover they have unknowingly violated it.