exam 3 - inorganic chemistry

Labile

Fast ligand substitution

Inert

Slow ligand substitution

If we have strong ligand field stabilization then the complex is kinetically…?

Inert

If configuration places electrons in orbitals that are anti bonding (eg set) or weak bonding, the substitution is…..

Labile

smaller radius —> stronger M-L bonds —> slower substitution meaning….

Inert

larger radius —> weaker bonds so….

Faster (liable) substitution

Ionic radius increases going down a period, meaning the larger, the radius, the…..

Faster the reaction more labile

Stronger ligand filed (stronger bonding) tends to make substitution….

Slower (inert)

Kinetic means what compared to thermodynamics ?

How fast vs how stable

remember a complex can be thermodynamically stable but kinetically Labile (or vice versa)

For an Oh complex, if substitution requires breaking a string M-L bond first this is what type of RXN and how quickly does it happen?

This is Dissociative rxn and this happens SLOW

If there is a ready path for ligand to associate or interchange, this is what type of RXN and how quickly does it happen?

Associative RXN and it happens FAST

Metal high charge/small radius = ?

Strong bonds

Low charge/larger radius = ?

Weaker bonds

Thermodynamics correlates to what equation

Kinetics relates to what equation

Ea= activation energy

A= frequency factor

R=gas constant

T=tempatute (K)

Higher Ea= ?

Slower reaction (smaller k)

Lower Ea=?

Faster reaction (larger k)

Labile complex’s have low or high Ea

Low Ea (their bonds are easier to break)

Inert complex’s have high or low Ea

High Ea, (their M-L bonds are very strong).

Half life = t(1/2)

Lifetime - average time before substitution

If we have a full lower energy orbital (t2g has all 6 e-) and an empty eg orbital (d6!) what does that mean in terms of reactivity

Indicates inert, and not reactive (or reacts very slowly)!

If we have a half -full lower energy orbital (t2g has all 3 e-) and an empty eg orbital (d3!) what does that mean in terms of reactivity

Inert, and not reactive (or reacts very slowly)

If we have a full lower energy orbital (t2g has all 6 e-) and eg has 1 electron (d7!) what does that mean in terms of reactivity

Think Jahn Teller distortion (d7 and high field). Labile and highly reactive

4d metal are ….

All LOW SPIN

Dissociate mechanism means what about bonds and donor atoms

Bond-breaking, RDS

Weaker donor —> more labile

Stronger donor —> more inert

Associate mechanisms mean what for bonds and donor atoms

Bond-making RDS

stronger donor —> faster (more labile)

Weaker donor —> slower (more inert)

D orbitals are gerade or ungerade with respect to inversion

D orbitals are GERADE

( s and d =gerade)

(p and f =ungerade)

No change in multiplicity and symmetry changed means

Allowed!

Change in multiplicity and no change in symmetry

Forbidden

high oxidation state and pi system mean

LMCT —> high molar absorbtivity