On average, how many piπ bonds does "O"_2^(+)O+2 have?

2 Answers
Feb 13, 2016

As mo theory there should be 1.5 pi bond

Explanation:

MO configuration of O_2^+O+2
enter image source here

Feb 14, 2016

You would have a bond order of 2.52.5 in "O"_2^(+)O+2. Remembering that "O"_2^(+)O+2 has one sigmaσ bond as well, you therefore have 1.51.5 piπ bonds on average.


BOND ORDER OF HOMONUCLEAR DIATOMICS

Bond order is a measure of bond strength, and suggests stability. It is half the number of bonding minus the number of antibonding molecular orbitals.

"Bond Order" = ("Bonding e"^(-) - "Antibonding e"^(-))/2Bond Order=Bonding eAntibonding e2

piπ bonds are made when all lobes of an orbital overlap in parallel (such as two 2p_x2px or two d_(xz)dxz orbitals, where the xx axis is toward you and the zz axis is upwards).

You can have optimal overlap, less than optimal overlap, or no overlap. Poorer bonding overlaps correspond with lower values of bond order. Or, less antibonding overlap corresponds with higher values of bond order (which is what applies here).

The structures of "O"_2O2 and "O"_2^(+)O+2 are:

DIATOMIC OXYGEN IS PARAMAGNETIC

While Valence Bond Theory suggests oxygen is diamagnetic, Molecular Orbital Theory correctly demonstrates that oxygen, "O"_2O2, is paramagnetic.

That means it has unpaired electrons. Specifically, two unpaired electrons, one in each piπ antibonding orbital (pi_(2px)^"*"π*2px and pi_(2py)^"*"π*2py), where the zz direction is along the internuclear axis.

The MO diagram for neutral "O"_2O2 is:

![https://upload.wikimedia.org/](useruploads.socratic.org)

When you take away one electron, you take it away from the highest-occupied molecular orbital. Since either the pi_(2px)^"*"π*2px or pi_(2py)^"*"π*2py can function as such (they are the same energies), one of these orbitals can lose an electron when we wish to form "O"_2^(+)O+2.

DETERMINING BOND ORDER

Naturally, "O"_2O2 has a bond order of 22 which corresponds nicely with its double bonded Lewis structure.

Two bonding electrons each come from the sigma_(1s)σ1s, sigma_(2s)σ2s, sigma_(2pz)σ2pz, pi_(2px)π2px, and pi_(2py)π2py molecular orbitals for a total of 1010. Two antibonding electrons each come from the sigma_(1s)^"*"σ*1s and sigma_(2s)^"*"σ*2s, and one each from the pi_(2px)^"*"π*2px and p_(2py)^"*"p*2py molecular orbitals for a total of 66.

(10 - color(red)(6))/2 = color(blue)(2)1062=2

When taking away one pi^"*"π* antibonding electron to form "O"_2^(+)O+2, we change the bond order to:

(10 - color(red)(5))/2 = color(blue)(2.5)1052=2.5

Since "O"_2^(+)O+2 has lost one of two antibonding piπ electrons, its bonds get less weak by half. So, instead of going from 11 piπ bond to 0.50.5 piπ bonds, it goes to \mathbf(1.5)1.5 \mathbf(pi) bonds.