Yeah, it's fairly easy to implement multiple dbs. the db class which is located in wp=db.php handles all of the db requiests. All you have to do is modify the class to direct the query to which ever db you wish.
In my cluster setup I had one main DB (Dilbert) which held the main blog a few stats tables and the user table that I modified to keep track of which cluster a user is on. I then had three clusters (Ratbert, Catbert, and Dogbert) which were a master database and a few slaves depending on the size of the cluster. The whole idea with the "clusters" is that I could take one cluster offline for maintenance and still have ~75% of the site running.
I also had a table on the main cluster that kept track of each cluster. Users, load, and cluster status. If something went wrong on a cluster of if it was down for maintenance the cluster would be given the status of read only. I then made a nice little plugin that checked the cluster status and made each blog "Read Only". Basicly the idead here is that if something is wrong with a server or database I don't want users messing around in their control panels or adding content in case I had to revert to a backup.