Memorize Inorganic chemistry

Inorganic Chemistry

Free Ion the d orbitals are

degernate

UV

higher energy transition between Ligand orbitals

Visible

lower energy transition between d orbitals fo transition metals

Chacaterstics of absorption leading to electronic transition 

1. number (electron conf)

2. position (wavelength/energy/logand field splitting)

3. Intenetisy “allownenes”” 

Lobes overlap

large electron repulsion (large energy)

lobes far apart

small electron repulsion

L

shape of the orbitals  (quantum number, the Toal orbital angular momentum of all electron) 

ml

orientation of orbitals

ms

orientation of electron spin

Number of Microstate equation 

N= n!(e!(n-e)!

S

the total spin angular momentum of all the electrons

L is 

spdfghi 

How to we electron arrangement symbol

2s+1 L

J value equation

L+S, L-S

Number of micro states for J equation 

SJ+1

HuNDS RULE

1. ground state have largest spin multicipity

2. two state with the same spin, so largest L is of lowest energy

3. Subshell is less than 1/2, the lowest J,

4. Subshell is more than 1/2, the highest J

UV Vis Transition and CD and MCD

Multiply the A1/A2/b1/b2 and see if its linear function or rotational. If electric dipole is allowed

Laporte selection 

transition between states of same parity (symmetry with respect to center of inversion) are forbidden d(centrosymmetic) p is noncetrosymmertci 

Spin Selection

transition between states of different spin mulitpicies are forbidden

Rules Relax

1. Vibration, changes symmetry (vibrionic coupling)

2. Tetrahedral complex absorb more strongly, p orbitals are more involved so it is loss of centrosymmetric

3. Spin orbit coupling, the interaction of particles spin with field created but its motion (Second and tHIRD row transition) → degernation orbitals split

T

triply degernation is assymetirc 

E

doubly degernation asymmetrically occupied state

A or B

non degenerate state (symmetrically occupied)

Increases the X axis for Tanable Sugano Diagram 

increases field strength 

Tetrahedral Diagram change

Holes make D10-n

LMCT

• higher oxidation state

• Metal is reduced

• Metal is lower in energy

• Ligand is higher in energy

• Ligands contain non bonding electron

• Transition correlated with order of electrochemical series

• more easily reduced the metal (more positive E∘E∘), the lower the LMCT transition energy (i.e., longer wavelength).

• As ligand electronegativity increases → LMCT transition energy increases.

MLCT

• low oxidation state 

• Pi acceptor Ligands(strong field ligand) 

• Metal is higher in energy

• Ligand is lower in energy

Fluorescence

no change in multiplicity

Luminescence

Re-emission of radiation after electronic excitatio

Ground state and excited states are neutral 

Not observed 

Excited is polar the ground is neutral

Lower in energy

Neutral excited states, polar ground states

higher in energy 

Ground and excited states are polar

higher in energy

Stimulated Emission Essential to a Coherent Light Source Equation

Change in E= hv

negative temerpature= 

physics for excited state 

Arrhenius Equation:

k=Ae^-Ea/RT or In k= In A - Ea/RT

Keg

Products/reactants

Labile

Fast (Eg anti bonding characters) 

Inert

Slow (no eg character)

Evidence of Dissovativr Mechanism

1. Oxidation state of central ion (slower ligand exchange)

2. Ionic Radius

3. Both leads to higher electrostatic attraction

Steric Crowding for Dissociative 

Easier for ligands to dislocation becuase steric crowding and strain to relieve the strain 

Dissociation Volume of Activation

Postive

Volume of Activation means

change in volume for the activated complex on forming the activated complex (transition state)

ML5=

K1 (ML5X)/ K-1(x)+k2(y)

Rate Law for interachnege if Large X and Y

Its kind like pseudo first order conditions

Evidence of Assocationmechansim

1. rate depends on incoming ligand

2. steric crowding decrease

3. the volume of activation is negative 

ML5XY=

k1 (ML5X)(y)= k-1 +k2

thermonduanmoc T dependence on Keg

In K = deltaH/RT + change in S/R

Square Pyramidal intermediate for trans ligand 

forms trans 

trigonal bipyramidal intermedia for trans

loss of stereochemistry form lambda and trans

Alternative trigonal bipyramidal intermidiea for trans

form cis complexes

cis ligand for square pyramidal 

from cis (retention) 

Trigonal biyramidal intermediate cis

los of stereochemistry forms trans delta and delta acarcater

Alternate trigonal bipuramidal intermixed (B is axial) 

cis character 

Square planar Rate Law

K1 (ML2TX)+ K2(ML2TX)(Y)

Trans AFFECT

CN, CO, C2H4> PH3, SH2> NO2-> I→ BR> CL> NH3, py > OH> h20

Inner Ligand (Birdgeing Ligand)

at least one ligand as to be labile

Outer Ligand 

Both ligands is inert 

Monodentate Ligand Dissociation

The kinetic chelate affects is not imprecate dub another

Multidentale ligand

if half a bidentate chelated dissociates, it is still tethered so re coordination is fast

10 7 nm = 

1 cm 

More positive reduction potential:

the species is easier to reduce (more oxidizing in its oxidized form).

How does ligand field strength affect E°?Strong-field (π-acceptor

) ligands stabilize the higher oxidation state → reduction less favorable → E° more negative.

Inner-sphere

(strongly bound, often π-acceptor): igands increase covalency and stabilize high oxidation states → E° more negative.

Outer-sphere (weakly bound, ionic)

ligands poorly stabilize high oxidation states → E° more positive.