Alex got real close.
High frequency sound coming from tweeters will interact with cabinet edges, causing small peaks and valleys in the frequency range of about 4 to 8 kHz. The exact frequencies are determined by the distance from the tweeter to the cabinet edge. This is called diffraction, and in effect, it creates new points of origin for sound in addition to the tweeter.
If the tweeter is centered in a tall narrow cabinet such as in many MTMs, there will be two identical tweeter-to-edge distances, with identical diffraction peaks and valleys that add up. If the tweeter is slightly off center there will be two slightly different tweeter-to-edge distances. They may generate more peaks and valleys than with a centered tweeter, but because they are at differing frequencies and won't add up, they will each be smaller in amplitude.
Dennis Murphy always prefers off-set tweeters in his designs because he can easily see the difference in his measurements. He is not certain that this makes an easily audible difference, but off-set tweeters are easy to make at no extra cost during construction, so why not do it.
The exceptions are speakers like the Philharmonic 3 or the Salk HT1 & HT3 where the tweeters are centered, but the cabinets are not rectangular, and the front baffles don't have parallel edges.
So, off set tweeters can make a measurable difference in a single speaker in mono. What happens in stereo? Are off-set tweeters better toward the outside or the inside? People wonder and argue which is better. I doubt if it makes any difference. Take your pick.
Edit: This explanation is, of course, an oversimplification. A longer discussion of cabinet edge diffraction can be read here
http://www.salksound.com/wp/?p=160#more-160.