My bet for Black would be Grunfeld/Sicilian and then the Spanish for White. A lot of these complications can be avoided, depending how your opponent responds, though. Pretty much any opening has lines that contain a lot of theory and multiple choices for plans. All three of these openings are known for rich, complicated middle games and large amounts of theory.
Best for complicatated positions?

The sicilian Sveshnikov or Najdorf come to mind, but you better like theory if you plan to play these openings. Another extremely complicated and theoretical monster is the Winawer poisoned pawn. It leads to a very unbalanced position which is usually quite sharp and very theoretical. As far as defences to 1.d4, some variations of the semi-slav are really sharp and complicated, aswell as the grunfeld and KID.

My problem with the Sicilian D is that they have been all over analized and so much theory is out there and so many players play it.. equally the Spanish (Ruy Lopez) ...
The Semi slav really gets complicated ... Is the Semi Slav D over analized and deep in theory?
What about the Alekhine defense? the Reti or the English opening? Do they tend to get a player into complicated positions?
Alekhine definitely tends to get complicated. I played a lot of games against an Alekhine specialist and had a chance to sharpen a lot of lines. Diabolically complicated.

I usually do well in the Alekhine better than any other defense... anything similiar against d4.... The reverse Sicilian has anyone run against it?
Who is this Alekhine specialist? ( send me private info so i can play against him if he is online).

The Semi slav really gets complicated ... Is the Semi Slav D over analized and deep in theory?
You're asking for the best openings that reach a complicated middlegame.
Those are exactly the openings that have the most theory.
If you don't want insane amounts of theory, either go for not quite best or not as complicated.
What are the best openings and defenses that usually lead into a complicated middle game or closed game?