Zita West's Guide to Getting Pregnant has a section on 'gender selection'. In brief, she mentions some laboratory research that shows that in lab conditions, female sperm (ie those carrying the X chromosome) tend to be heavier, slower swimmers, but have a stronger structure so don't disintegrate as quickly; male sperm (with the Y chromosome) tend to be smaller and lighter, so faster swimmers, but disintegrate more quickly.
This research hypothesises (can't prove) that if you wanted a baby girl, you should have intercourse 3 days before ov, so that the male sperm would have disintegrated, and the female sperm would be left. If you wanted a boy, you should have intercourse a few hours before ov, so that the male sperm beat the female sperm to the egg.
As West points out, there are two huge flaws to this method:
1) It works on averages - the average female sperm is slower than the average male sperm, and there are more female sperm left after a couple of days (in the lab) than male sperm. NOT there are no male sperm!
2) If you try to time intercourse for no less than 3 days before ov, or no more than a few hours, you might not get pregnant at all, as it's impossible to predict ovulation with that much certainty...
So she says it might be worth a try if you'd like to test out the theory and you're not in a hurry to get pregnant, but if you really want a baby, then you should be aiming for well-timed intercourse in the two days before ov and the day of ov.
Sorry that's so long - I've just condensed a whole chapter!