My opinion (for whatever it's worth) is that the more sources of sound arround you, the more realistic will be the sense of being in the middle. I realize this sounds like something the Sphinx from Mystery Men would say, but it seems to fit the situation.
In your case, I don't recommend you buy a "true" center and "surround" speakers. For the best pure music experience, each speaker in the system would be exactly the same model number.
You would want at least want a larger surround than would be normal for a movie. The drivers should be the same size as your front drivers and have similar frequency response, even if you go with bookshelves in the back. In the case of the 750's they use a 5 1/4 driver, so you could use probably use a pair of 150's as surrounds, but I wouldn't go with the RSS 300's (they just don't reach very low at all)
In an HT surround system, you are mainly looking to provide higher frequencies from your surrounds, as those frequencies are the ones humans best use to detect movement. In the end, for HT, you are actually better off with smaller speakers (like the RSS 300's)
In a "music" system, however, the different INSTRUMENTS are on different channels, so you never really know if you will be reproducing an oboe or bass sax from one of the surrounds. It just depends on what the mixing guy was feeling like that day. If you go with smaller surrounds, you risk not being able to faithfully reproduce all the possibilities that might be coming out.