When Electro attacked Spider-Man in Times Square the entire incident was being broadcasted live. Tony Stark was watching the News and when he heard Spider-Man speaking he knew exactly who it was because Peter had interned at Stark Industries. Iron Man showed up at the scene to help but Electro and Spider-Man were already gone. The sad thing is Tony had the technology capable of restraining Electro and he had the medical capabilities needed to save Harry. If only he had shown up earlier.