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Chemistry 3820 (Fall 2006) Figures for PART III Crystal Field Theory

Many simple inorganic compounds form crystals that can be regarded as a close-packed arrangement of ions with the counterions occupying the holes. NaCl or ScN ZnS or AgI fcc of Cl- with Na+ in octahedral (O h ) holes fcc of S2- with Zn2+ in tetrahedral (T d ) holes

NaCl

ZnS

Na

Cl

In a crystal (e.g. ZnS or ScN), the metal cations occupy a particular hole in the lattice, and the ligands are arranged with a well-defined symmetry (defined by a certain point group) around the metal.

---------------------------------------------------Experimentally Determined Values of o (units = 1000 cm -1 , values in brackets are for low spin complexes)

2006 - Dr. Paul G. Hayes University of Lethbridge

Chemistry 3820 (Fall 2006) The Spectrochemical Series of Ligands

For octahedral transition metal complexes, o varies depending on the nature of the ligands, which can be arranged in the following spectrochemical series (so called, because the series can be determined using UV-visible absorption spectroscopy): weak field ligands (small o ) strong field ligands (large o)

I- < Br- < S2- < SCN- < Cl- < F- < OH- < OH2 < MeCN < NH3 < PR3 < CN- < CO < NO+ good -donors OK -donors -donors good -acceptors

Using Ligand Field Theory instead of Crystal Field Theory, we have seen that ligands can be -donors, -donors or -acceptors, and that the ability of a given ligand to act as a -donor or -acceptor has a large effect on the magnitude of o. As a result, the order of ligands in the spectrochemical series closely follows their behaviour as -donors, -donors or -acceptors. ------------------------------------------------------------------------------------------The Spectrochemical Series of Metals o depends not only on the nature of the ligands, but also on the metal and its oxidation state. The spectrochemical series for metal ions (approximate) is shown below: Mn2+ < Ni2+ < Co2+ < Fe2+ < V2+ < Co3+ < Mn4+ < Mo3+ < Rh3+ < Ru3+ < Pd4+ < Ir3+ < Pt4+

This series is not quite as regular as the spectrochemical series of ligands, but there are obvious trends: (1) For a given metal and ligand set, o increases with increasing oxidation state (Co2+ < Co3+ etc.). Explanation - Metal ions in a higher oxidation state have greater polarising power. As a result, bonding becomes more covalent and less ionic. (2) For a given oxidation state and ligand set, o increases down a group (Co3+ << Rh3+ < Ir3+). Explanation - M-L bonding is more effective for larger 4d and 5d orbitals relative to the 3d orbitals. - Also, higher effective nuclear charge on the metal. (3) For a given oxidation state and ligand set, o varies irregularly across the TMs (groups 3 to 12). Explanation - Depends on a variety of factors! 2006 - Dr. Paul G. Hayes University of Lethbridge

Chemistry 3820 (Fall 2006) Why is the Series of Ligands or Metals named the Spectrochemical Series ? Variations in the size of o can often be seen visually: e.g. for [CoIII X(NH3)5 ]n+ (a d6 complex).

X IClNH3

n 2 2 3

Colour of the complex Purple Pink Yellow

eg

Colour absorbed
o

Yellow Green Blue

d t2g

The colour of the complexes above results from promotion of an electron from the t2g orbital to the eg* orbital. The energy of light absorbed therefore corresponds to the size of o. [Note: this type of simple treatment can only be applied in certain cases (e.g. d1 or d9 complexes and octahedral 3d 4 complexes with a d or d6 configuration). For other configurations, it is necessary to consult a Tanabe-Sugano diagram and apply a more rigorous treatment see later]. For complexes with a single absorption in the visible region of the spectrum, the colour of light absorbed can be determined from the colour wheel (the colour of the light absorbed is found opposite the colour of the complex) Since the order of energy is blue > green > yellow, then the NH3 complex can be seen to have a larger o than the Cl- complex, which has a larger o than the I- complex. From the colours of such complexes, it has been possible to build up a series o ligands which is f arranged in order of increasing o. Since the effect of the ligands on the size of o is a visible change, the resulting series of ligands is called the spectrochemical series.

2006 - Dr. Paul G. Hayes University of Lethbridge

Chemistry 3820 (Fall 2006) CFSE for all possible d-configurations Configuration d0 d1 d2 d3 d4 d5 d6 d7 d8 d9 d10 t2g3 eg1 = 0.6 o t2g3 eg2 = 0.0 o t2g4 eg2 = 0.4 o -P t2g5 eg2 = 0.8 o -2P t2g6 eg2 = 1.2 o t2g6 eg3 = 0.6 o t2g6 eg4 = 0.0 o High Spin t2g0 eg0 = 0.0 o t2g1 eg0 = 0.4 o t2g2 eg0 = 0.8 o t2g3 eg0 = 1.2 o t2g4 eg0 = 1.6 o -P t2g5 eg0 = 2.0 o -2P t2g6 eg0 = 2.4 o -3P t2g6 eg1 = 1.8 o -3P Low Spin

P = pairing energy required to overcome Coulombic repulsion when 2 electrons occupy the same orbital. In all cases, if o > P, then a low spin configuration is favoured energetically.

CFSE for different d-electron configurations

2006 - Dr. Paul G. Hayes University of Lethbridge

Chemistry 3820 (Fall 2006) Hydration Enthalpy for divalent cations of the 3d transition metals M2+(g) M3+ (aq) M2+(g) + 6 H2O(l) [MII(H 2O)6 ]2+ (aq)

2006 - Dr. Paul G. Hayes University of Lethbridge

Chemistry 3820 (Fall 2006)

Jahn-Teller Distortion of Octahedral Complexes (Along the Z-axis)

2006 - Dr. Paul G. Hayes University of Lethbridge

Chemistry 3820 (Fall 2006)

Extreme Elongation of the Z-axis of an Octahedral Complex: Square Planar Orbital Energies

2006 - Dr. Paul G. Hayes University of Lethbridge

Chemistry 3820 (Fall 2006)

Crystal Field Splitting Diagram for Tetrahedral Geometry

OCTAHEDRAL

TETRAHEDRAL

In tetrahedral complexes inter-axial orbitals point more directly at the 4 ligands more of an unfavourable interaction between the ligand electrons and those of the metal higher in energy

Axial orbitals point less directly at the 4 ligands less of an unfavourable interaction between the ligand electrons and those of the metal lower in energy

t2

d orbitals

t ~ 4/9 o

t is much smaller than o partly because none of the metal orbitals point directly at the ligands, so overlap is less efficient.

e M [ML4]

2006 - Dr. Paul G. Hayes University of Lethbridge