While chemical properties are determined by the electronic structure of an element, that structure is, in turn, caused by the number of protons in the nucleus of the element (which is the atomic number). And it isn't the number of electrons that characterises and element (strip electrons from an iron atom to give Fe2+ or Fe3+ and we still recognise the element as iron.)
What matters in radioactive decay is what changes in the nucleus. If a nucleus loses two electrons it becomes a different element and the electronic structure will be different. Usually the orbital electrons are ignored as what happens during the decay involves the nucleus only. After the nuclear decay the orbital electrons may rearrange in chemical processes.
We don't normally account for the orbital electrons in nuclear reactions as the orbital electrons are engaging in chemical not nuclear processes and. Besides, there are nuclear processes that involve electrons (neutrons in some nuclei can emit electrons and protons in others can capture them: these processes do involve electrons but it would be confusing to mix accounting for them with accounting for the chemical changes that result from things happening to orbital electrons).
Nuclear chemists only count what happens to the nucleus and ignore the ensuing chemical changes.