Crystal stabilization energy (CFSE) CFSE = Energy lowering in the "crystal field" of the ligands, e.g., in an octahedral or tetrahedral complex Compare.

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Presentation transcript:

Crystal stabilization energy (CFSE) CFSE = Energy lowering in the "crystal field" of the ligands, e.g., in an octahedral or tetrahedral complex Compare the CFSE for [Cr(CN) 6 ] 4- and [Cr(H 2 O) 6 ] 2+ What are the rules for high spin vs. low spin?

Crystal stabilization energy (CFSE) Hydration enthalpies of M 2+ ions Can you explain the trends?

Magnetic Susceptibility Molecules and ions that contain unpaired electrons are paramagnetic We can count the number of spins by measuring the susceptibility magnetic moment: µ ≈ µ spin = [n(n+2)] 1/2 µ Bohr What µ s values would you expect for Ni 2+ and Cu 2+ ?

When octahedra are distorted, the resulting geometries change the energies of the e g and t 2g orbitals (break degeneracy) Non-octahedral complexes Octahedron Elongated octahedron Square pyramid Square plane

d 8 (and d 9 ) are special electron counts for square planar complexes Non-octahedral complexes ΔOΔO dx 2 -y 2 dz 2 dxy dxz dyz Which metals (with which ligands) will form square planar complexes?

Square planar complexes are important in homogeneous catalysis Non-octahedral complexes Catalytic hydrogenation of olefins using Wilkinson's catalyst

What splitting pattern would you predict for a tetrahedral complex? Non-octahedral complexes

Tetrahedral complexes Co[CoCl 4 ] + 12 H2O ---> 2 Co(H 2 O) 6 Cl 2 (deep blue, tetrahedral CoCl 4 2- ) (light pink, octahedral [Co(H 2 O) 6 ] 2+ ) Why are tetrahedral complexes more strongly colored than octahedral ones?

Jahn-Teller Effect Complexes with unequal populations of electrons in upper (antibonding) orbitals distort to lower their energy [Cu(OH 2 ) 6 ] 2+ [Cu(OH 2 ) 5 ] 2+

Chelate and Macrocyclic Effects Multidentate ("chelating") ligands make very stable complexes What is different about these reactions?? Metal-en complexation [Co(H 2 O) 6 ] NH 3 ⇌ [Co(NH 3 ) 6 ] H 2 O [Co(H 2 O) 6 ] en ⇌ [Co(en) 3 ] H 2 O

Chelate and Macrocyclic Effects Chelating ligands EDTA 2,2'-bipyridine = bpy acetylacetonate = acac

Chelate and Macrocyclic Effects Macrocyclic ligands Valinomycin 18-crown-6 Heme b