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Chapter 11

Coordination Complexes

• Unlike most organic compounds, many coordination compounds have vivid colors.

– These vivid colors are due to the electronic transitions between the d-orbitals of the metal.

• The energy levels of d electron configurations, however, are usually more complicated than might be expected since the electrons in the atomic orbitals interact with each other.

Absorption of Light

• Complementary colors – if a compound absorbed light of one color, the complement of that color is observed.

– [Cu(H2O)6]2+ has a blue color. What is absorbed?

**• Beer-Lambert Absorption Law
**

• log(Io/I)=A=εlc (define variables) • In a common absorption spectrum, the A is plotted versus wavelength or cm-1 (1/λ).

**Quantum Numbers of Multielectron Atoms
**

• In order to understand energy transitions between states with more than one electron, we need to understand in more detail how these electrons interact with each other. • Each conceivable set of individual ml and ms values constitutes a microstate of the configuration.

– How many microstates in a d1 configuration? – Examine the carbon atom (p2 configuration)

• Determine the electron configuration and quantum numbers. • Independently, each of the 2p electrons could have one of six possible combinations. The two electrons, however, are not independent of each other.

**Interaction between Electrons
**

• In any microstate, the individual orbital magnetic moments (related to ml) and the spin magnetic moments (related to ms) will interact resulting in an energy state or term for the configuration.

– Commonly, a number of microstates will contribute to a single term (degeneracies).

**• This is an approximation using the one-electron wave mechanical mode.
**

– Works well for 1st and 2nd row transition metals.

**Term Designation (Free-Ion)
**

•

2S+1

L

– L and S relate to the overall orbital and spin angular momenta for the system (or state). – L = overall orbital angular momentum quantum number.

• Discuss possible values (analogous to the l quantum number). • L is related to the vectorial addition of vectors taken from the l quantum number. • Discuss the permitted ways in which the l values can combine (Figure 20, Carter).

**Overall Orbital Angular Momentum Quantum Number, L
**

• The vectorial addition produces the possible terms for a given configuration. • For a given term, the magnitude of the resultant angular momentum is fixed, [L(L+1)]1/2(h/2π). • The vector for the momentum can have a number of allowed orientations.

– A partial lift of degeneracy by the magnetic field. – Allowed orientations for a given term are associated with the overall magnetic quantum number, ML.

• ML = L, L-1,….-L

**Overall Orbital Angular Momentum Quantum Number, L
**

• ML relates to the orbital multiplicity or orbital degeneracy (Each has projection equal in magnitude to ML(h/2π)).

– What are the allowed orientations for a D term?

**• In the Russell-Saunders scheme, ML = ∑ml.
**

– An ML value can be assigned to each microstate.

**• Therefore, a given L value must arise from a complete set of microstates with the 2L+1 values.
**

– Examples

**Overall Spin Quantum Number, S
**

• Spin state of the term. • 2S+1 – spin multiplicity of the state.

– S=0, 1, 2

**• Like L, S can be obtained by vectorial addition of the spin angular momentum vectors (related to s or ms).
**

– Magnitude [S(S+1)]1/2(h/2π)

**• S is related to an overall spin quantum number, MS.
**

– MS = S, S-1,…-S (2S+1 values) – Indicates the ‘allowed’ orientations of the vector relative to an applied magnetic field. The produces the spin degeneracy in a spin state.

**Overall Spin Quantum Number, S
**

• Magnitude of the spin angular momentum is [S(S+1)]1/2(h/2π), but its projections on a particular axis in the allowed orientation are given by MS(h/2π).

– Russell-Saunders scheme, MS=∑ms

In Summary

• Any given term with L and S values arises from a set of microstates that has the necessary 2L+1 values of ML and also the necessary 2S+1 values of MS. • Value of the term

– L = largest possible value of ML

• Let’s do the d2 configuration.

Determining Microstates

• Determine the number of microstates for a triplet P. What are the allowed ML and MS values? • Determine the number of microstates for a doublet D. What are the allowed ML and MS values?

– It is sufficient to designate the microstates by x (only the number is important).

**• Number of microstates in a given free-ion term is equal to (2L + 1)(2S +1).
**

– Row multiplied by column

**Reducing a Microstate Table/Configuration into Its Free-Ion Terms
**

• Notice that each term is composed of a rectangular array of microstates.

– This process is shown for a p2 configuration in Table 11-4. – The spin multiplicity is same as the number of columns of microstates. – The # of rows to include in the rectangular array is equal to +L → -L (number of values).

• (2L+1)(2S+1) Do the p2 and d2 configurations.

**Term of the Lowest Energy
**

• The ground term (lowest energy) has the highest spin multiplicity. • If two or more terms share the same maximum spin multiplicity, the ground term is the one having the highest L value. What is the term with the lowest energy for the d2 configuration?

**Spin-Orbit Coupling
**

• There is also spin-orbit coupling wherein the spin and orbital angular momenta couple with each other.

J = L+S, L+S-1, L+S-2,….|L-S| (no negative values) J is a subscript on the right side of the L quantum # – Determine the spin-orbit coupling in the 1S and 3P free-ion terms. Designate these with J.

• Page 388

**Lowest Energy Term Including Spin-Orbit Coupling
**

• For subshells (such as p2) that are less than half-filled, the state having the lowest J value has the lowest energy. For subshells that are more than half-filled, the state having the highest J value has the lowest energy.

– Determine the lowest energy state for the p2 configuration.

**Electronic Spectra of Coordination Compounds
**

• Absorption spectra in most cases involve the d orbitals of the metal. • Identifying lowest energy term (quickly)

– Sketch the energy levels showing the d electrons. – Spin multiplicity of lowest-energy state equal highest possible number of unpaired electrons +1. – Determine the maximum possible value of ML (∑ms) for the configuration. – Combine steps. High- and low-spin d6 configurations in octahedral symmetry.

**Reducing the Symmetry of the Free Ion by a Ligand Field
**

• The orbital term symbols for the free atom/ion are identical to the symbols for the appropriate symmetry species in the spherical group, R3 (show Table).

– There are no inherent symmetry restrictions on possible orbital degeneracies.

• D – fivefold degeneracy (ML = ?) • F – ???

Correlation Table

**Reducing the Symmetry of the Free Ion by a Ligand Field
**

• When a ligand field is imposed, however, there are restrictions placed on the maximum orbital degeneracy.

– In an octahedral complex, the maximum degeneracy is 3 (Ttype IR’s, look at table). Orbital degeneracies present in the free ion must be split.

• All term symbols will be redefined by the new symmetry. • Upon reducing the symmetry, the free-ion term can be treated as a reducible representation composed of irreducible representations in the appropriate character table.

**Reducing the Symmetry of the Free Ion by a Ligand Field
**

• The total number of microstates, Dt, remains the same. • Do the d1 configuration.

– What does this split into when an octahedral field is imposed? – How many microstates are possible when imposing the ligand field? The new ligand-field terms will retain the original spin multiplicities found in the free-ion terms. Examine

**Correlation Diagrams – Relating Electron Spectra to Ligand Field Splitting
**

• Examine the correlation diagram for a d2 configuration in an octahedral ligand field.

– Far left (absence of ligand field) – the free-ion terms. On this side, the ligand field has very little influence.

• Examine the previous table.

**– Far right (strong ligand field) – the states are largely determined by the ligand field.
**

• Observed before in the crystal field and ligand field discussion.

• In real compounds, the situation is somewhere in the middle.

**Splitting of Free-Ion Terms
**

• Irreducible representations are produced.

– Examine the correlation diagram and the Oh table.

• Table 11-6

– Each state has symmetric characteristics of that IR. – IRs are also obtained from the strong-field limit configurations (right side of table).

• The IRs on the right and left sides must ‘correlate’.

**Selection Rules for Transitions
**

• Transitions between states of the same parity are forbidden.

– Laporte Selection Rule

**• Transitions between states of different spin multiplicities are forbidden.
**

– 4A2 → 4T1 and 4A2 → 2A2 Discuss how the rules are relaxed on the expected absorption intensities.

**Tanabe-Sugano Diagrams
**

• Special correlation diagrams useful in the interpretation of electronic spectra.

– Lowest energy state is plotted along the horizontal axis.

∀ ∆o/B (field strength)

**– Vertical axis is the measure of the energy above the ground state
**

• E/B B = Racah parameter, a measure of the repulsion between terms of the same multiplicity.

– Lines connecting states of the same symmetry cannot cross.

A d2 Configuration, [V(H2O)6]3+

Electron Configurations

• The diagrams of d2-d8 are illustrated in Figure 11-7. • There is a vertical line near the center of d4-d7 diagrams. What does the vertical line represent? What happens once the line is crossed? • In some cases, the absorption bands are off-scale (x-axis) or obscured by the charge-transfer bands (discussed later). • Discuss the terms for the configurations. They are not the same as observed for the orbital terms.

**Jahn-Teller Distortions
**

• Spectrum of the [Ti(H2O)6]3+ complex.

– The complex has a d1 configuration (Fig. 11-8). – Go over terms for the configurations. – Why are there two overlapping bands?

• If degenerate orbitals are asymmetrically occupied a distortion will occur to remove the degeneracy.

**• Jahn-Teller distortion is usually only significant for asymmetrically occupied eg orbitals.
**

– The others cannot be resolved. – The most common distortion is along the z-axis (elongation).

**Symmetry Labels for Configurations
**

• Symmetry labels for electron configurations match their degeneracies.

– T = triply degenerate asymmetrical state – E = doubly degenerate asymmetrical state – A or B = nondegenerate Do a few without Jahn Teller splitting/distortion.

• Effect of a D4h field.

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