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If you think about it, even though the 4s orbital is listed first on the periodic table, the 3d orbital still comes before it in the order of electron orbitals. Thus, when you calculate the electron configuration of the cation, you have to take it from the outmost (4s) orbital rather than the 3d orbital. The principal quantum number of the 4s orbital is higher, so always go by that rather than the "order" of the orbitals (s, p, d, f) because you might get confused!
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