Advanced Inorganis Exam 2

This occurs when the metal donates from its d orbitals to the ligand’s HOMO orbital

back donation

This occurs when the ligands donate from its HOMO to an empty metal orbital

sigma donation

This is the energy required to put two electrons in the same orbital

pairing energy

This is the energy that accounts for t2g stabilization and eg destabilization NOT pairing electrons. This is the energy difference between the metal ion in an octahedral coordination geometry in a spherical field.

splitting energy

This has filled p orbitals (no pi star), ligand donates to metal, the t2g orbital is higher in energy but the splitting energy is lower. The energy in d-d transitions is lower, complexes are blue-green color, and they have weak field ligands and are high spin.

pi donor

This has empty pi star orbitals, the metal donates to the ligand, the t2g energy is lower, the splitting energy is higher, the d-d transitions have higher energy, complexes are a yellow-orange, and they have strong field ligands, usually low spin

pi acceptor

This is used to describe nonlinear molecules that may distort their geometry to remove the degeneracy of unequally occupied orbitals and lower the energy of the complex. This occurs when the d orbitals are not filled evenly.

jahn-teller effect

According to the Jahn-teller effect, if electrons occupy dz² more, what happens?

elongation

According to the Jahn-teller effect, if electrons occupy dx²-y², what happens?

compression

The more _________ the CFSE, the more stable the complex and lower energy than the spherical unsplit case. They are less reactive, slower ligand substitution, and have stronger metal-ligand interaction.

negative

When the CFSE is ________ or ___, there is little stabilization or even destabilization from splitting, often more labile (reactive)

positve, zero

What strength of field ligands cause small splitting of d orbitals?

weak

What strength of field ligands will cause large splitting of d orbitals?

strong

What type of field ligands are high spin?

weak

What type of ligands are low spin?

strong

These types of ligands are weak field ligands, have filled p orbitals (no pi*), have a ligand → metal pi donation, increases t2g energy, smaller splitting energy, lowers the energy for d-d transitions (longer wavelength), have an observed color of blue/green, and are high spin. Examples include halides and hydroxide

pi donor ligands

These types of ligands are strong field ligands, have empty pi* orbitals, have metal → ligand pi backbonding, decreases t2g energy, larger splitting energy, raises the energy for d-d transitions (shorter wavelength), have an observed color of yellow/orange, and are low spin. Examples include CO and CN^-.

pi acceptor ligands

The ______ the metal, the more diffuse the d orbitals, resulting in stronger interactions, and larger splitting of the d orbitals

larger

The _____ the oxidation state, the closer the ligands are pulled together, resulting in stronger interactions, and larger splitting of the d orbitals

higher

This coordination has smaller splitting than an octahedral geometry because

• fewer ligands, less interaction

• orbitals are off axis and don’t point directly to ligands

• weaker overall field

tetrahedral

This coordination has a larger splitting than octahedral complexes because:

• stronger interactions in the plane

• dx²-y² orbital has direct overlap with ligands, resulting in strong repulsion

• larger energy separation

square planar

Most tetrahedral complexes are ___ spin.

high

Most square planar complexes are ___ spin.

low

In general, orbitals that have enrgy difference greater than __-__ do not combine favorably

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