According to periodic table, Nitrogen and phosphorus are present in the same group, so it may assumed that both will behave same in terms of bonding with other elements but it is not true in all cases. Phosphorus being the member of 3rd period has vacant 3d orbital which tend to take part in hybridisation like in PCl5, but nitrogen being the member of 2nd period has no such option of 3d orbital involvement in hybridisation. That's why NCl5 does not exist but PCl5 exist.
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