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It is because an atom with low ionization energy would loose an electron easily and the high electronegative atom has the tendency to attract electrons.

The high electronegative atom would easily be able to get the electron from such an atom which has very low ionization energy.

This is the case with Alkali metals and and Halogens.

Alkali metals are highly electropositive and have low ionization energy and hence loose electrons very easily whereas Halogens are highly electronegative and have the tendency to attract electrons towards themselves.

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