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to point-field ligand charges to explain the break in degeneracy in transition metal d-orbitals upon forming complexes. In an octahedral complex if 6 ligand point charges are applied to the Cartesian coordinates then, by considering the effect of this increase in localized charge density, it can be seen that the eg set (the dx2-y2 and dz2) becomes higher in energy (by +3/5ΔO) and the t2g set (the dxy, dxz and dyz) decreases in energy (by -2/5ΔO). There is also a pairing energy value (P) to consider, if electrons are paired that weren’t in the original state, the energy of pairing them is shown as +P. The pairing energy does not vary in a simple predictable manner with dn. When P is larger than ΔO the complex will be high spin (weak field case) and vice versa, when P is smaller than ΔO the complex will be low spin (strong field case). Crystal field theory fails to explain why changes in ligand can give different complex properties, for example [Ni(H2O)6]2+ being green yet [Ni(NH3)6]2+ is blue. It also fails to explain the properties of large or charged ligands as it assumes every ligand to be a point charge, an assumption most flawed with larger or charged ligands. This is because crystal field theory is not a bonding argument, to develop a bonding argument for transition metal complexes molecular orbital theory (MO Theory) must be utilized. Molecular Orbital Theory of Octahedral Transition Metal Complexes Metal-ligand bonds are covalent bonds in which the ligand (a Lewis base) donates both bonding electrons to a metal centre (a Lewis acid). For a metal to accept electrons from a ligand orbital the orbitals involved must be of comparable energies and of the same symmetry and in most cases the electrons being donated are found as a lone pair on the ligand. For the metal the valence orbitals are easy to identify; 1st Row; 3d, 4s, 4p 2nd Row; 4d, 5s, 5p 3rd Row; 5d, 6s, 6p The orbital size increases down the group. For an octahedral complex, when considering the MO diagram, it is easiest to consider the πsymmetry and σ-symmetry orbitals separately. Considering only orbitals of σ-symmetry only the following are considered (taking a first row element); 4px, 4py, 4pz, 4s, 3dz2 and 3dx2-y2 These are the orbitals that point along Cartesian axes and so are σ-symmetry. The lone pairs are, if in need of identification, simply notes as the σx, σ-x, σy, σ-y, σz, σ-z. There are therefore 6 metal orbitals of interest, 6 ligand orbitals, and 3 π-symmetry orbitals of nonbonding alignment. Since there are 15 orbitals being combined there must be a total of 15 orbitals formed in the molecular orbital diagram, the 6 metal orbitals and ligand orbitals of σ-symmetry will form 6 bonding orbitals and 6 anti-bonding orbitals leading to the following molecular orbital diagram;
The 6 lone-pairs of the ligand orbital fill the bonding orbitals (the a1g, t1u and eg), any electrons on the metal are then put into the t2g and e*g set suggesting that the e*g is in fact not too anti-bonding in nature. Note that the t2g-eg gap derived in crystal field theory is actually between the non-bonding t2g set and the anti-bonding eg set, since the electrons in the bonding molecular orbitals are closer in energy to the ligand group orbitals the bonding orbitals are ligand-centred, this is the only reason crystal field theory works, by coincidence. Considering π-bonding in Transition Metal Complexes If a ligand, for example a halide, is to be placed with a lone pair being donated to a metal centre then the remaining p-orbitals will be perpendicular to the metal-ligand bond and so be in a position to π-bond with the t2g orbitals on the metal. The effect of this π-bonding is weaker than of σdonation and so the MO diagram shown above isn’t entirely changed by inclusion of π-bonding, simply modified. For each ligand there are 2 p-orbitals of π-symmetry and so 12 in total, these transform as t1u, t1g, t2u and t2g in symmetry. Since there are no orbitals of t1g or t2u symmetry on the metal these are non-bonding and can be ignored, similarly although there is a weak interaction between the t1u π-orbital and that of the metal p-orbital the energy difference is too large for its impact to be considered and so it is also ignored.
This leaves 3 t2g orbitals in the ligand group orbitals and 3 t2g orbitals on the metal, and so a combination of 3 bonding and 3 anti-bonding orbitals are formed. If the π-orbitals on the ligand are occupied then it is a π-base and will donate ligands to the metal. If the π-orbitals are empty then the ligand is a π-acid and will accept electrons from the metal. A ligand will usually be π-basic if the energy of the metal orbitals is greater than the energy for the t2g orbitals on the ligands e.g. F-, Cl-, I-, Br- and oxoanions (-SO4, -NO3). This leads to the following MO diagram;
eg* Δo t2g Δo t2g*
t2g Here Δo decreases as a result of π-bonding from a π-basic ligand.
A ligand will usually be π-acidic if the energy of the metal orbitals is lower than the energy of the t2g orbitals on the ligands, e.g. –CO, pyridine, -CN. This gives rise to the following MO diagram; t2g* eg* Δo t2g Δo eg*
t2g Upon bonding with a π-acidic ligand the splitting energy, Δo, increases. If the t2g orbitals of the ligand are to be unoccupied, it often means they are anti-bonding orbitals (as is the case in –CN or –CO) and so by bonding with the metal back-bonding occurs, here the d-orbital electrons of the metal are placed into the anti-bonding orbital on the ligand, increasing the strength of the metal-ligand bond but weakening the bond within the ligand, a process that can be useful in the identification of substances. The Importance of Δo Values The value of Δo is important in explaining the nature of metal covalence orbitals, the factors determining the size of Δo are;
1)the electrostatic (crystal) field -generated by metal and ligands -values are proportional to charge on metal i.e. [Mn(H2O)6]2+ - Δo=8,500cm-1 [Ni(H2O)6]2+ - Δo=8,500cm-1 [Co(H2O)6]3+ - Δo=20,700cm-1 The electrostatic strength increases with the charge on the metal leading to a stronger M-L interaction and so a larger Δo value. 2)position of the element on the periodic table -for d-elements as the triads are descended (i.e. Co->Rh->Ir) ionic radii increases -Δo values increase down the triad by 30-50% each time -as such high spin complexes are very rare for 2nd or 3rd row metals When considering [M(NH3)6]3+; Metal Cobalt Rhodium Iridium Δo value (cm-1) 23,000 – orange 33,000 – yellow 41,000 – colourless
Metal complexes in high oxidation states also become more stable as the table is descended, for example OsO4 and RuO4 are stable whilst FeO4 is unknown. 3)σ-bonding, the strength of the M-L interaction -this is crucial in determining the energy of the eg level -strong bases are often good σ-donors however there is also a stearic role, NH3 is a much weaker base than N(C2H5)3 however ammonia is a better ligand as it is smaller, this is called ‘ligand-ligand interaction’ 4)π-bonding -determines the energy of the t2g orbitals The effects of 3 and 4 can be combined to give the spectrochemical series. For a given metal and in order of increasing Δo; I-<-SCN<Cl-<-NO3<F-<H2O<SCN-<NH3<bipyridine<H-<R3P<-CN<CO The beginning of the series consists of π-bases and throughout they become gradually more and more π-acidic. Tetragonal Distortion – Square Planar Complexes In comparison to an octahedral arrangement of ligands, a square planar complex can be considered an octahedron with the z-axis ligands removed. To explain why analogous compounds can display different geometries, i.e. NiCl4- is tetrahedral and PdCl4- is square planar, the energies of the systems must be compared, to consider the effect of removing the z-axis ligands on the energies of the orbitals in a transition metal complex a process called ‘tetragonal elongation’ is performed.
By pulling along the z-axis any orbital with z-character will decrease in energy while the others will increase in energy leading to a further split state. dx2-y2 dz2 dxy dxz and dyz By continuing this elongation and finally removing the z-axis ligands the square planar complex can be shown to have an energy diagram as follows; dx2-y2 Δo Δo dxy dz2 4/3 Δo
dxz and dyz Nickel and palladium 2+ are both d8, since nickel is in the first row of transition metals it is more able to maintain a high-spin configuration, since Cl- is low in the spectrochemical series this also leads towards low Δ values. For palladium, as it is second row, it will naturally have a larger Δ value thus making the dx2-y2 strongly anti-bonding, this makes it much more likely for Pd2+ compounds to form low-spin complexes and so square planar geometry is observed. The Jahn-Teller Effect ‘For non-linear molecules, if the ground state is ‘orbitally degenerate’ the system will distort in order to remove this degeneracy.’ e.g. Cu2+ - d9; dx2-y2 dz2 dxy dxz and dyz dz2 dx2-y2
The 9th electron could occupy either the dz2 or dx2-y2 equally, this is an example of an orbitally degenerate state. While it would be expected that [Cu(H2O)6]2+ would have an octahedral geometry it is actually found that two of the bonds trans to each other (i.e. the 2 z-axis Cu-H2O bonds) are longer than the other four bonds. This is a result of the Jahn-Teller effect, the degeneracy of the dz2 and dx2-y2 orbitals is broken by elongation along the z-axis to give the following energy diagram; dx2-y2 dz2 dxy dxz and dyz
For the Jahn-Teller effect to occur there must be an appropriate vibrational mode (e.g. a symmetric ‘breathing’ mode in which all bonds move in and out together does not remove degeneracy, only a symmetric stretch outwards along one axis as shown above). The Jahn-Teller effect can also apply to other d-configuration species. For example Ti3+, which is d1, in the hydrated [Ti(H2O)6]3+;
dx2-y2 dz2 dxy dxz and dyz This is a triply degenerate ground state, similar to the above example but the electron occupies the t2g set and not the eg set. A tetragonal elongation along the z-axis here would still leave two degenerate states (the dxz and dyz would remain the same energy). It is possible to then perform a second elongation along a second axis, this is called a rhombic distortion, however it is much simpler to instead perform a tetragonal compression – a compression across the z-axis. This increases the energy of orbitals with z-character and decreases the energy of those with no z-character to give the following energy diagram; dz2 dx2-y2 dxz, dyz dxy This leads to 2 shorter bonds trans to each other and 4 longer bonds in [Ti(H2O)6]3+. The Jahn-Teller effect is more pronounced for ‘centered degeneracies’, that is σ-orbitals give strong Janh-Teller effects but π-orbitals give weaker distortions. If a ligand has a strong π-basic character (e.g. amido) it is strongly t2g based and so a Jahn-Teller effect may be observed. The Jahn-Teller effect can be observed for; d1, d2, d4, d5 (low spin), d6(high spin), d7 and d9 species. X-ray crystallography can provide direct measurements of metal-ligand bonds thus proving the JahnTeller effect, but it can also be seen in UV-visible spectroscopy. The UV spectrum of [Cu(H2O)6]2+ shows an asymmetrical band which contains a ‘shoulder’, this is actually 2 bands overlapping and is an indicator of the Jahn-Teller effect as it displays the 2 possible transitions similar in energy, from the dxz or dyz to the dx2-y2 and the dxy to the dx2-y2; dx2-y2 dz2 dxy dxz and dyz
Reactions of Inorganic Complexes Labile and Inert Complexes The terms labile and inert refer to the kinetic stability of a molecule, an inert complex is kinetically stable and changes ligands slowly, they tend to have a high CFSE. Labile complexes change ligands quickly and tend to have a low CFSE. Hard and Soft Acid And Base Theory (HSAB) Hard Acids Small, highly charged, metal cations Low polarisability* Good π-acids Examples; H+, Li+, Na+, Mg2+, Al3+, Sc3+, Ti4+, Co3+ Lanthanides, actinides High oxidation state metals Hard Bases High electronegativity Low polarisability* Not easily oxidized Poor π-acids, often π-bases Examples; Amines, ammonia O- donors (H2O, -OH, ethers, alcohols) FSoft Acids Soft Bases Large zero/low charge metal atoms or cations Low electronegativity High polarisability* High polarisability* Good π-bases – participate in back-bonding Easily oxidized Examples; Good π-acids of d-electrons Ru and Os (0, II), Rh and Ir (I) Examples; Pd and Pt (II and IV), Cu (I), Ag (I), Hg (I), Pb (II) Phosphine, Arsine, Stibine, Sulfide, Selenide I->Br->ClAlkyls, alkenes, alkynes, CO, CN, isocyanides, some metals *Polarisability is defined by μ=αE where μ is the induced dipole moment, E the electric field strength and α is the polarisability (J-1 C2 m2), soft donors/acceptors have high α values As a general rule hard acids prefer to associate with hard bases and soft acids with soft bases. The Rates of Ligand Substitution Reactions Metal ions are solvated in solution - complex formation reactions are therefore ligand substitution reactions. The rate of formation of a ligand substitution can be written step-wise (with K1, K2 etc. relating to the first and second substitution respectively) or generally as; MLn-1+L⇌MLn
For reactions occurring in water [H2O] is considered constant. Since K1, K2 etc. are constants, their products are also constants.
So in general;
In general K1>K2>K3 and so forth, this is under the assumption that metal ligand bond energies do not change very much along the series. The values steadily decrease due to a number of factors; -statistics. If there are less H2O ligands to displace and more L groups to displace then an incoming ligand can displace either, at first H2O is more likely but eventually L becomes more likely. -steric forces in cases where bulky ligands are displacing less bulky ligands -charge. Charged ligands become increasingly more difficult to introduce on electrostatic grounds, increasing the charge density will also tend to reduce LFSE values. When this trend is not observed it can be due to a change in electronic structure or a change in the coordination geometry of the species. In the case of [Fe(H2O)6]2+ becoming [Fe(bipy)3]2+ K3 is much larger than K1 and K2. This is due to the nature of bipyridine, it is a strongly π-acidic chelating ligand that generates large Δ values. Upon addition of the third ligand molecule Fe2+ actually moves from a high spin to a low spin case due to this increase in the Δ value, the low spin case is preferred due to an increase in the CFSE. This, alongside the chelate effect contributes to the increase in K3 otherwise unexpected. The chelate effect is largely entropic in nature. If a chelating ligand were to displace water on a solvated ion more moles would be produced as a result and so entropy increases. The chelate effect is important in analytical chemistry, for use in compleximetric titrations, and biochemistry, in most enzyme systems. There an enzymes such as enterobactin that are such good chelating ligands there are specific enzymes tailored to release the metal ions they chelate too. There is a further effect, the macrocyclic effect. A cyclic ligand contains 3 or more donor atoms in a large ring.
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