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During hybridization of d-orbitals why the $d_{z^2}$ and $d_{x^2-y^2}$ orbitals are used up before the $d_{xy}$, $d_{yz}$ and $d_{zx}$ ?

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The rotational frame of reference which defined which axis is the z-axis is changed such that $d_{z^2}$ and $d_{x^2-y^2}$ are hybridized first is a convention / practice.

In theory (meaning mathematically), you should be able to get equivalent geometry if you used the other d orbitals for hybridzation.

Basically the donut thing is weird enough we try to fold it in so we can deal with the more normal cloverleafs as leftovers.

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  • $\begingroup$ Of course hybridisation with d orbitals doesn't really happen, not even in a theoretical way. $\endgroup$ – Martin - マーチン May 11 '20 at 9:08

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