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Does that happen because 3p already has a bond?

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    $\begingroup$ Vanadium has a valency of 5 to start with, so transferring an electron from a 3p orbital into a 3d orbital would lead to a valency of 6 not 7. $\endgroup$ – Philipp Nov 23 '14 at 13:59
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Vanadium has a stable valency of 5.
Electrons cannot be transferred from $3p$ orbital to $3d$ orbital as the $3p$ orbital is completely filled and has attained stability.
It requires high energy so as to transfer electrons from $3p$ orbital to $3d$ orbital.
Hence,Vanadium has a valency of 5 only and not of 7 or 6.

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