Chemistry 3211 – Coordination Chemistry Part 3 Ligand Field and Molecular Orbital Theory

Electronic Structure of Six and Four-Coordinate Complexes Using Crystal Field Theory, we can generate energy level diagrams describing the relative energies of the different metal-based d-orbitals in an octahedral crystal field. This assumes only electrostatic interactions and does not consider any covalent bonding (σ, π or δ) interaction or orbital overlap. This gives rise to two sets of orbital energy levels. The doubly degenerate eg set consists of the axial orbitals dx2-y2 and dz2 and is higher in energy than the triply degenerate t2g set consisting of the interaxial dxy, dxz and dyz orbitals. The energy difference is Δo.

Distortions from the ideal octahedral environment cause variations in the orbital energy levels. For example, if we start pulling away one of the ligands along the z-axis, ultimately removing it to form a five-coordinate square pyramidal geometry, this partly removes an unfavourable (according to CF theory) interaction in the z-direction. All orbitals with a z-component (dz2, dxz and dyz) fall in energy. The others go up in energy. This gives rise to the energy level splitting diagram shown below.

C. M. Kozak – Chemistry 3211


Note the large energy gap between the dxy and dx2-y2 orbitals. copper(II). Only when coordinated to strong field ligands such as CO or CN. is smaller than Δo (by a crude approximation. but the dxy.s. On the other hand. distortion from the ideal octahedral geometry results in a new distribution of d orbital energy levels.s. which has nine d electrons.Removing the other ligand on the z-axis has the same effect. d4 complexes) a tetragonal distortion may be energetically advantageous.does a large enough ligand field splitting occur. Pd(II) and Au(III). two or three electrons (as in l. Pt(II). These distortions may arise as a result of steric interactions among the ligands. illustrates y2) and so have 16 electrons rather than 18. such as those found for Rh(I). forms six-coordinate complexes that usually depart considerably from true Oh symmetry and often show significant tetragonal distortions. which gives rise to large ligand field stabilization by going to low spin square planar complexes. d8. such as [Ni(CN)4]2-. Four coordinate complexes are the second most abundant and the same kinds of arguments can be applied to these species. For example. Figure 20-10 in Housecroft and Sharpe 2 the crystal field splitting parameters for common geometries. Therefore. Ligand field stabilization energies for tetrahedral complexes can be calculate in exactly the same way as for octahedral complexes. The common occurrence of square planar 4d8 and 5d8 complexes relates to the high value of the ligand field splitting parameter for these heavier transition metals. Low-spin d7 and high-spin d4 six-coordinate complexes may show a similar distortion.6ΔT Because there is no centre of inversion in a tetrahedron. if the eg set is occupied by one. 3d8 metal complexes. d8 complex may be large enough to encourage the pairing of two electrons in a dz2 orbital. M.where X is a halogen are generally tetrahedral because the ligand field splitting is generally smaller for the first row transition metals. Z t2 0.s. ΔT is generally 4/9 the magnitude of Δo). for a regular tetrahedron. ΔT. the distortion of a h. dxz and dyz orbitals approach the ligand location more closely than do the dz2 and dx2-y2 orbitals. the orbital sets are labelled t2 for the triply degenerate set and e for the lower energy doubly degenerate set (the orbital designations do not include the parity label g or u). leading to the energy level diagram for a square planar complex. None of the metal d orbitals points exactly at the ligands. As a result. Therefore. square planar complexes are almost exclusively those of d8 metals (all metal orbitals are filled except the dx2nd Ed. C. resulting in the formation of a square planar complex. A tetrahedral geometry can be described by superposition within a cube. Ir(I). Tetragonal Distortions and the Jahn-Teller Effect As described above. As a special case. Extension of the z-axis and compression of the remaining axes reduces the energy of the eg(dz2) orbital and increased the energy of the eg(dx2-y2) orbital. but we have to take into account the different order of the d-orbital energies. this may lead to the loss of two ligands on the z-axis and the formation of d8 square planar complexes. and the crystal field splitting. Kozak – Chemistry 3211 2 . d7. or indeed from the nature of the metal ion itself. the only differences being the order of occupation (e before t2) and the contribution of each orbital to the total energy (-3/5 ΔT for an e electron and +2/5 ΔT for a t2 electron).4ΔT X Y e ΔT 0. Effectively. d9 and h. such as [NiX4]2. the splitting of the d orbitals is inverted compared to that of an octahedron.

the complex will distort so as to remove the degeneracy and achieve a lower energy. It states that if the ground state electronic configuration of a non-linear complex is orbitally degenerate. Essentially.e. for d9. it does not predict the preferred distortion. where two of the ligands are removed entirely. high spin d4 and low spin d7 electron configurations.9 of S & A 4Ed). Recall that in constructing molecular orbitals from atomic orbitals. d4 dxz Ligand Field Theory Although crystal field theory is useful in approximating energy levels in transition metal complexes. So then. We have already noted that the ligand field splitting parameters. the number of orbitals must remain constant (i. that is.s. The Jahn-Teller effect can only identify an unstable electron configuration.8 and 2. Kozak – Chemistry 3211 3 . it resonates between the two orbitals and this destabilizes the complex. the fact that it ignores any possible covalent bonding interactions between the metal and its surrounding ligands is rubbish. The unpaired electron can occupy either of the dz2 or dx2-y2 orbital because they are energetically degenerate.For six-coordinate systems possessing an odd number of electrons in the eg orbitals. dx2-y2 dz2 dx2-y2 z-axis elongation dz2 dx2-y2 z-axis elongation dx2-y2 dz2 Barycentre dxy dyz dxz dz2 dxy dyz dxz Barycentre dxy dyz d9 dxz dxy dyz l. This results in a lowering of the overall ligand field stabilization energy for the complex. The distortion to give a square planar complex. why does the spectrochemical series arrange the ligands the way it does? What is common with the strong field ligands that allows them to increase Δ? Does the electron configuration in the atomic and molecular orbitals in these ligands have something to do with it? Of course it does! You are recommended to revise your understanding of basic Molecular Orbital theory for simple diatomic molecules (covered in Sections 2. we place the more electronegative element on the right hand side and that its AOs are lower in energy. Remember also that for most heteronuclear diatomic C. is an extreme case of tetragonal distortion. if the geometry is physically distorted and we allow one metal-ligand bond axis to lengthen. number of MOs equals the number of AOs). An octahedral d9 complex has three electrons in its eg set of orbitals. Δ. Therefore. M. the paired electrons will preferentially occupy the lower energy orbital and the unpaired electron will populate the highest energy orbital. but should not be confused with the JahnTeller distortion because d8 electron configurations are not orbitally degenerate. Typically. are strongly dependant upon both the metal AND the ligand (thus the spectrochemical series of ligands). d7 dx2-y2 dxz dz2 dx2-y2 z-axis elongation dz2 dxy dyz dxz Barycentre dxy dyz h.s. these tetragonal distortions can be attributed electronically to the Jahn-Teller effect. However. this will remove the degeneracy of the eg set and one orbital will become lower in energy than the other.

but more on that later! C. The highest occupied molecular orbital (HOMO) in N2 is of σ symmetry (a lone pair which can act as a Lewis base to form a coordinate covalent bond) whereas the HOMO in O2 is of π* symmetry. Note the difference in the arrangement of the σ2p and π2p orbitals between O2 and N2.e. and indeed they are.complexes. M. The bonding modes exhibited by N2 and O2 should therefore be slightly different. orbital mixing occurs (i. which will be useful in explaining various aspects of Ligand Field/Molecular Orbital theory for metal complexes. there is a hybridization of the atomic s and p orbitals because of similar energies). Kozak – Chemistry 3211 4 . Recall that for O2 (and F2 and Ne2) the energy difference between the 2s and 2p orbitals is large and therefore no s-p orbital mixing is observed. Below are molecular orbital diagrams for three simple diatomics.

1 or 2). It uses symmetry-adapted linear combinations (SALCs) of metal-ligand interactions and. but especially in molecules where orbitals with antibonding character are occupied.on O. Usually electronegativities are a good indication of the direction and magnitude of the dipole on a molecule. Each of these orbitals has local σ symmetry with respect to the M-L axis. or charged. ligands are found throughout coordination chemistry and metal carbonyl compounds are particularly important as catalysts in organic synthesis. Kozak – Chemistry 3211 5 . M. the vacant π* orbital LUMO can act as an electron pair acceptor capable of forming metal ligand π bonds. However.1 Debye) with the δ. Such ligands are termed “sigma donor ligands” and can be neutral. which combines aspects of Crystal Field theory with the more rigorous treatment of bonding given by MO theory. It is diamagnetic. orbitals or groups of metal orbitals that are labelled by a particular Mulliken Symbol can only interact with a ligand set of orbitals that is described by the same label. Sigma (σ) Bonding Consider an octahedral complex in which each ligand has a single valence orbital directed toward the central metal atom. C. as the name suggests. which are given labels that describe their symmetry (subscripts g or u. O has one more). such as fluoride. such as ammonia. e. The resulting Symmetry Labels (also called Mulliken Symbols) are used to now describe sets of orbitals in a complex. and their multiplicity (a or b. the metal orbitals divide by symmetry into four sets. with a bond order of 3 (C≡O) and has a HOMO of σ2p (weakly antibonding) symmetry and a lowest unoccupied molecular orbital (LUMO) of π*2p (strongly antibonding) symmetry. relies on some application of symmetry elements and group theory to produce a viable bonding model. NH3. Also.charge on carbon. These types of bonding in metal complexes are described by Ligand Field theory. we would expect a large dipole moment with δ. rather than just the atomic orbital. As a result. things are not so straightforward. CO ligands are good Lewis bases and are σ donors at the carbon atom. or carbonyl. t). Since O is far more electronegative than C. Therefore.Molecular Orbital Diagram for CO Carbon monoxide. CO is isoelectronic with N2 (C has one less electron than N. CO actually has only a small dipole moment (0. F-. therefore the MO diagram is very similar to that of N2. In a strictly octahedral environment.

Pauli principle and Hund’s rule. We are now treating all six ligands as a group. These combinations are shown below. Bear in mind that these are not specifically s or p atomic orbitals any more. dyz) does not possess suitable symmetry to undergo σ-bonding interactions with the ligand SALCs. but only the orbitals. Therefore. particularly those of period 2 and 3 (n quantum number ≤ 3) in the main group. Molecular orbitals for the resulting complex are formed by combining SALCs and metal orbitals of the same symmetry type. which will be discussed later. Thus. Kozak – Chemistry 3211 6 . the greatest contribution to the molecular orbital of lowest energy is from atomic orbitals of lowest energy. However. py. dxz dx2-y2. C. where we are only considering ligand s orbitals to keep things simple. dz2 Symmetry Label a1g t1u t2g eg Degeneracy 1 3 3 2 Six symmetry-adapted linear combinations of the six ligand σ symmetry orbitals can also be formed. tiu and eg) and six ligand SALCs. dyx. these combine to form 6 bonding and 6 antibonding MOs. For the resulting energy levels. dxz. For most ligands. However. The metal t2g set remains non-bonding in this scenario. or that there is no ‘ligand electron’ density present near the central metal atom.Metal Orbital s px. the electrons provided by the ligands are largely confined to the ligands in the complex. M. atomic or molecular. it does possess π symmetry. The resulting MO diagram can now be populated with electrons according to the Aufbau process. only the t2g set (dxy. the six bonding MOs of the complex are mostly ligand-orbital in character. which exhibit σ symmetry with respect to the metal-ligand bond axis. Among the metal orbitals. the ligand σ orbitals are derived from AOs with energies much lower than those of the metal d-orbitals. pz dxy. this is not to say that there is no metal character in these MOs. Since we have six metal orbitals that can be broken down into three groups according to their symmetry (a1g. These six bonding orbitals can accommodate the 12 electrons provided by the six ligand lone pairs.

enough delocalized MOs C. if any. has a d0 electron configuration. With several d orbitals (as well as s and p orbitals) available in the valence shell. Therefore. suggesting the metal ion. which are mainly metal in character anyway. The t2g and eg* (which is now of antibonding symmetry with respect to the M-L bond) are empty in this diagram. non-bonding metal t2g set and the higher energy. the frontier orbitals of the complex are the non-bonding. Δo. Kozak – Chemistry 3211 7 . M. antibonding eg set. The diagram below shows how the SALCs of the ligand orbital sets combine with the metal orbitals to produce molecular orbital energy levels (the MO diagram) of an octahedral ML6 complex. the metal based d electrons tend to reside largely on the metal atom. most reactions of metal complexes occur at the metal centre. The octahedral ligand field splitting parameter. Therefore. because most bonding (and therefore “chemistry”) occurs in the valence (or “frontier”) orbitals of a compound. M. whereas in CFT Δo is purely a metal d orbital separation. in this approach is called the HOMO-LUMO separation. or HOMO-LUMO gap.The d electrons of the metal centre. entirely metal based t2g orbitals and the antibonding eg orbitals. occupy the lower energy. In summary. LFT explains very well the problem that Werner faced regarding the ability of a metal to bind numerous ligands (secondary valence). It is approximately the splitting of the metal d orbitals caused by the ligands.

therefore. Also. they can accommodate even more ligand electrons and.can be constructed to accommodate all the electrons needed to bind the ligands. can easily have coordination numbers higher than 6. Kozak – Chemistry 3211 8 . since lanthanides have f orbitals as well. M. C.

Kozak – Chemistry 3211 9 . These ligand π orbitals may be populated or vacant and. the bonding is SYNERGIC: σ-donation to the metal strengthens π-backbonding to the ligand. The effect of this bonding on Δo depends on where the electron density is going. For π-acceptor ligands. Conversely. and π-donation from the metal to the ligand strengthens the σ-donor component of bonding. then they may form π MOs with the t2g set of metal orbitals. which allows increased πbackdonation. therefore.Pi (π) Bonding The above diagram ignores any potential π bonding that may be present (the t2g set is non-bonding). may act as electron donors or acceptors as shown in the diagram below. M. which allows more σ-donation from the ligand to the metal. π-backdonation reduces the amount of electron density on the metal. C. If the ligands in a complex have orbitals with local π symmetry with respect to the M-L axis (a t2g ligand SALC). This is because σ-donation leads to increased electron density on the metal.

the π donor ability of CO is very small. Δo is increased due to the “pushing down” in energy of the bonding t2g symmetry molecular orbitals. Kozak – Chemistry 3211 10 . The result is that ligand electrons occupy the bonding t2g MO. they lie higher in energy than the metal d orbitals. Because these π acceptor ligands are typically of antibonding character with respect to the ligand atoms. NR2.A π donor ligand has filled orbitals that have π symmetry around the M-L axis. which their MO diagrams we have described previously. M. Examples of π donor ligands include Cl-.and H2O. while the metal electrons now occupy the antibonding t2g MO set. Because of the resulting energy correlation. As a result. A π-acceptor ligand is a ligand that has filled π orbitals. It also has empty π∗ orbitals which are close enough in energy to the metal d orbitals to allow population. These bonding combinations lie slightly lower in energy than the metal d orbitals themselves. and its bonding to metals is dominated by its π acceptor character along with its σ donor ability (see diagram below). which has been raised in energy. Examples of ligands that possess orbitals of this appropriate energy are CO and N2. Ligands that are π acceptors increase Δo. Ligands that are π donors decrease Δo. the bonding combination lies lower than the ligand orbitals and the antibonding combination lies above the energy of the d orbitals of the free metal (figure below on the left). The bonding π orbital of MO is populated and is largely localized on the O atom because O is more electronegative than C. hence the lower energy π bonding orbital is mostly O in character. OH-. C. The energies of these orbitals are similar to those of the metal d orbitals and the ligand has no vacant low energy π orbitals (strictly speaking these are of π* symmetry). These all turn out to be low in the spectrochemical series (weak field ligands) that lower Δo. they form molecular orbitals of t2g symmetry which are largely of metal d orbital in nature. This means that when they form molecular orbitals with the metal t2g orbitals. which are much lower in energy than the metal t2g orbitals. The antibonding π* orbital of CO has its largest amplitude on C and has appropriate symmetry and energy to overlap the t2g orbitals of the metal. The full π orbitals of the π donor ligands lie lower in energy than the partially filled d orbitals of the metal.

but cannot effectively act as π donors to the metal centre. strong π acceptors are high in the series due to their ability to increase Δo. electron-electron repulsion further hinders any π donor ability from the CO ligand. are high in the series. The Cr0 centre is a 3d6 configuration. When π bonding is taken into consideration. The 6 CO ligands each donate two electrons to the metal centre via σ bonding. but also because the metal d6 centre has its t2g set populated by metal based electrons. C. Below is the resulting molecular orbital (MO) diagram for an octahedral complex with strong πacceptor ligands (e. partially because of their energies being much lower than the appropriate symmetry metal t2g set.g. like H. Strong π donors are low in the spectrochemical series due to their lowering effect on Δo. M. The π bonding symmetry orbitals of the ligands are also populated.The spectrochemical series can now be put in perspective on account of the σ and π binding ability of the ligands.and CH3-. Kozak – Chemistry 3211 11 . Strong σ donors. Cr(CO)6).

the stability of organometallic compounds (those possessing metal-carbon bonds) is strongly attributed to this effect. In transition metal complexes. this complex has 18 electrons that participate in bonding. Although a large number of exceptions to this rule are found in classical coordination chemistry. Each ammine ligand is a two electron donor. M. Therefore. this “18 electron rule” is similar to the “octet rule” used in main group chemistry. C. the metal “back-donates” this electron density into the CO π* orbitals.The antibonding π* orbitals of the CO ligand are vacant and are low enough in energy to undergo orbital overlap with the populated metal t2g set. Kozak – Chemistry 3211 12 . hence [Co(NH3)6]3+ possess 6 + (6×2) = 18 electrons. Werner studied Co3+ ammine complexes because of their stability. In total. The Co3+ ion has a 3d6 configuration. Complexes possessing 18 bonding electrons are particularly stable.

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