As Alex pointed out, the short answer is no. What's going on with your code is this: when a and b are already bound variables in the current scope, (a, b) means "take the values of a and b and construct a tuple from them."
Therefore,
(a, b) = ...
is equivalent to
(new Tuple2(a, b)) = ...
which is obviously not what you want (besides being nonsensical).
The syntax you want (ability to assign to multiple variables at once) simply doesn't exist. You can't even assign the same value to multiple preexisting variables at once (the usual syntax "a = b = ..." that's found in many other languages doesn't work in Scala.) I don't think it's an accident that vals get preferential treatment over vars; they're almost always a better idea.
It sounds like all of this is taking place inside of a loop of some kind, and doing repeated assignments. This is not very idiomatic Scala. I would recommend that you try to eliminate the usage of vars in your program and do things in a more functional way, using the likes of map, flatMap, filter, foldLeft, etc.