Hans Bethe 1906 - 2005.

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Presentation transcript:

Hans Bethe 1906 - 2005

Crystal Field Theory – metal-ligand bonds are viewed as entirely electrostatic (ionic) CFT Ligand Field Theory – crystal field theory that is adjusted for covalency (metal-ligand bonds are more covalent than ionic) LFT

gerade – any orbital whose symmetry labels remain unchanged upon performing an inversion ungerade – any orbital whose symmetry labels switch upon performing an inversion

s-orbitals are gerade, g p-orbitals are ungerade, u

*-orbitals are gerade, g

all 5 d-orbitals are gerade, g

Barycenter Barycenter – zero point energy between t2g and eg orbital sets. It is a “center of gravity” energy reference point for complex

M ML6 o

3/5 o o -2/5 o

o -

Consider the electron configuration of [Ti(H2O)6]3+ Ligand Field Stabilization Energy – decrease in energy gained (relative to the unsplit, degenerate state) due to d-orbital splitting LFSE

Determine the LFSE (in units of o and 10Dq) for [Cr(NH3)6]3+

Determine the LFSE (in units of o and 10Dq) for [Zn(H2O)6]2+

Determine the LFSE (in units of o and 10Dq) for [Fe(NH3)6]3+

Weak field (high-spin) Strong field (low-spin) Δoct < pairing energy Δoct > pairing energy

Magnitude of Δo (extent of d-orbital splitting) depends on three factors: 1. Identity of metal itself 2. Oxidation state of the metal in the complex 3. Identity and number of ligands attached to the transition metal All three combine to determine if the complex goes strong or weak field

Trend of Δoct energies for [M(NH3)6]3+ where M= Co, Rh, Ir

The Spectochemical Series I- < Br- < S2- < -SCN- (M attached to S) < Cl- < F- < C2O42- < H2O < -NCS- (M attached to N) < CH3CN < NH3 < en < bipyridine (bpy) < phenanthroline (phen) < NO2- < PPh3 < CN- < CO I-  H2O are known as weak field ligands. They cause a small split in Δo. -NCS-  en is a gray area. The magnitude of Δo caused by these ligands are certainly larger than the weak field ligands above, but the identity and oxidation state of the metal will typically determine whether the complex goes strong field or weak field. bipyridine (bpy)  CO are known as strong field ligands. They tend create a large enough Δo to drive complexes to strong field.

Determine the number of unpaired electrons and LFSE (in units of o and 10Dq) for [IrCl6]2-

Determine the number of unpaired electrons and LFSE (in units of o and 10Dq) for [CrCl6]4-

Determine the number of unpaired electrons and LFSE (in units of o and 10Dq) for [Cr(CN)6]4-

Determine the number of unpaired electrons and LFSE (in units of o and 10Dq) for [Fe(H2O)6]2+

Determine the number of unpaired electrons and LFSE (in units of o and 10Dq) for [Fe(H2O)6]3+

Is [Ti(H2O)6]3+ a strong or weak field complex ?