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Just to confirm - I've just checked and Red, Yellow, Green and Blue (by RGB and HSV definitions) are DEFINITELY NOT located at equidistant 90 degree intervals around the wheel.
I bet the colour theory behind the kuler hue wheel is very interesting. What is this model/theory?
According to our color guru, kuler uses a red-yellow-blue color wheel, the same as Illustrator CS3's color wheel. kuler offers a subset of Illustrator's new feature called Live Color, which lets you create even more color harmonies based on rules.
To me it looks as if it's built off of a red-green, yellow-blue opponent process scheme, as those are the four colors at 0, 90, 180 and 270 degrees on the wheel. There's a wiki link for it, but basically, the idea behind this is that there are only four truly unique hues to our sense of perception--these two pairs of opposites--and to our eyes/brains all other colors are built in reference to these two sets of unique hues. This idea goes back to a guy named Edward Hering and was long considered pseudo-science but in the last 50 years we've found information pathways in the retina that process color in just this way.
The HSV circle found in the mac os color picker lays hues out along it's circumfrence so that if you add any two points on opposite sides of the circle (say, red with cyan, or green with magenta) they'll cancel out and you'll get white or grey. Complimentary hues that kuler gives won't mix to neutral--they're based off of a separate, but possibly equally important way in which the eye responds to light. To my eye at least it gives some wonderful results.