Feel free to disregard this solution as subtracting a list from an Index does not preserve the order of the original Index, if that's important.
In [61]: df.reindex(columns=pd.Index(['x', 'y']).append(df.columns - ['x', 'y']))
Out[61]:
x y a b
0 3 -1 1 2
1 6 -2 2 4
2 9 -3 3 6
3 12 -4 4 8