Why structure of PCl5 is possible but not of NCl5
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PCl5 forms five bonds by using the d-orbitals to "expand the octet" and have more "places" to put bonding pairs of electrons. NCl5 does not exist because there are no d-orbitals in the second energy level. Therefore there is no way to arrange five pairs of bonding electrons around a nitrogen atom.
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Nitrogen is a 2nd period element which no vacant d-orbital whereas Phosphorus is the element of 3rd period which has vacant d-orbital. Hence Phosphorus can form bonds with 5 Chlorine atoms but Nitrogen can't.
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