Well, as has been repeatedly brought up on this site, chemistry is a subjective. I also think its pretty early on (in what will hopefully become a seven year run) to decide how we want things to turn out. Also having been a fan of former shows produced and written by the current show runners, they seem to specialize in stories that tell the journey of relationships. If you're familiar with either Alias or Fringe, main characters started out in solid relationships, suffered a great loss of that significant other, initially find support and friendship with someone they work with, which leads to an even stronger bound. That might not be where they are going, but I'm hoping that it is. At the beginning of Fringe I had no idea of how much I'd end up enjoying Olivia and Peter, especially when Anna Torv's (Olivia) husband (Mark Valley) played the (dead, but not so dead) love of her life for entire first season. IMO the writing of Peter and Olivia's journey had as much to do with their story as did the supposed "chemistry" between the actors. As for Sleepy Hollow, I'm wiling to wait and see where they intend to take us.