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The spectrochemical series

H&C p. 721

so should have the lowest charge density and so produce the smallest splitting   Yet CO is a strong field ligand and F.should have the greatest charge density and so produce the highest splitting CO is not charged.p-bonding  The spectrochemical series cannot be explained by crystal field theory or a s-bonding LFT model  F.a weak field ligand .

 . Need ligand field theory. e. halide ions From the metal to the ligand.Effect of p-bonding  The answer is p-bonding   From the ligand to the metal. p-back-bonding  p-bonding cannot be described by an electrostatic model such as crystal field theory.g.

t2u. 785 . t1u.p-bonding between CO and a metal  There are TWELVE available ligand p-orbitals since we have 6 ligands each of which has 2 p* orbitals   one in the plane of the board the other out of the plane  These give TWELVE symmetry based combinations with symmetry labels t1g. and t2g H&C p.

and t1u. The s-bonding MOs span a1g. eg.Interaction with the s-bonding MOs  The ligand p-bonding combinations interact with the bonding MOs of the s-bond picture altering the MO picture.   . so is no longer non-bonding. The t2g metal orbital set (which was non-bonding in the s-bond picture) now has a ligand p-bonding combination with which it can interact. Of these only t1u can interact with the corresponding ligand pbonding orbital set.

567 .The t2g ligand orbital set interacts with the non-bonding metal t2g d-orbitals ligand p-orbitals MO bonding combination MO anti-bonding H&S p.

Why does it matter?   explains the spectrochemical series origin of the 18-electron rule    tells us when the rule will be obeyed tells us when the rule will not be obeyed tells us how to deal with geometries other than octahedral. square planar. .g. e.

238-240 . are (relatively) low in energy  * * t2g* t2g  Interact with the s-bonding molecular orbitals (off-screen and can ignore) and the metal t2g set   the new t2g MOs contain the electron pairs from the ligand p-donor set forming the p-bond the new t2g* MOs contain any metal d-electrons  Doct is now from t2g* to eg* and is smaller S&A p.Effect of a p-donor interaction on the HOMO and LUMO and size of Doct  The donor orbitals must be filled – how else could they donate an electron pair? Filled orbitals.

therefore (relatively) high in energy  t2g  Interact with the metal t2g set    the new t2g MOs contain any metal d-electrons forming the pback-bond the new t2g* MOs are above eg* Doct is now from t2g to eg* and is larger S&A p. 238-240 .Effect of a p-acceptor interaction on the HOMO and LUMO and size of Doct  t2g* * eg* The acceptor orbitals must be empty – how else could they accept an electron pair? Empty orbitals.

The spectrochemical series  p-bonding interactions can explain the ordering of ligands in the spectrochemical series p-acceptor ligands are strong field  p-donor ligands are weak field  H&C p. 721 .

[W(Me)6] (12e-)  3 non-bonding orbitals so system doesn’t care if they’re filled or not  up to 18 electrons allowed   [Mn(H2O)6]2+ (17e-) [Fe(H2O)6]2+ (18e-)  2 weakly anti-bonding orbitals are accessible  At a push complex can accommodate up to 22 electrons  [Ni(en)3]2+ (20e-) S&A p.g. 238-240 .The 18-electron rule in ML6 In the absence of p-bonding  6 bonding orbitals  Complex needs 12 electrons to fill them and achieve lowest energy  e.

238-240 .g.The 18-electron rule in ML6: Effect of a pacceptor t2g* * eg*  t2g are now bonding  3 additional bonding orbitals  t2g  Complex needs 18 electrons to fill all bonding MOs and achieve lowest energy e. [W(CO)6] (18e-) S&A p.

Square planar complexes L L  L M L Crystal field splitting can be derived by considering electrostatic repulsions between the metal d-electrons and the ligand donor pair Ligand field theory MO diagram can be derived using symmetry  .

Metal dx2-y2 orbital overlaps with ligand orbital set having b1g symmetry .

py and dz2. dx2-y2 orbitals 4 metal-d based bonding/non-bonding/weakly anti-bonding orbitals orbitals D Metal dorbitals  Total 8 bonding/nonbonding orbitals  Therefore need 16 electrons Miessler & Tarr p 434 Metalligand bonding orbitals .Square planar complexes and the 18 electron rule  Need 4 s-bonding orbitals.   symmetry considerations make these involve the s. px.