Question
Why do phosphines have a high trans effect? (Hint: Consider the way in which they are bonded to a transition metal ion.)
Step 1
" The trans effect refers to the influence that a ligand has on the rate of substitution of another ligand in a coordination complex, particularly in octahedral complexes. Ligands that exhibit a strong trans effect can stabilize certain geometries and influence the Show more…
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Phosphine ligands (PR3) are stronger field ligands than amines (NR3). To rationalize why this effect is strong: (a) Draw the d-orbital splitting in a hypothetical sigma-only situation, where the donors are the lone pairs on P. (b) Antibonding orbitals on phosphine accept electron density from metals similarly to CO. Draw a metal d-orbital and a generic phosphine antibonding orbital, noting how the orbital phases interact.
Phosphine ligands (PR3) are stronger field ligands than amines (NR3). To rationalize why this effect is strong: (A) Draw a MO diagram including antibonding phosphine orbitals, just like for a hexacarbonyl complex (simple diagram with 8 MOs in the middle). (B) Amines have antibonding orbitals that have a very similar shape to the phosphine antibonding orbitals. If the symmetry is the same, why don't amine ligands accept electron density from metals?
Although the cis configuration is known for $\left[\mathrm{Pt}(\mathrm{en}) \mathrm{Cl}_{2}\right]$, no trans form is known. (a) Explain why the trans compound is not possible. (b) Suggest what type of ligand would be required to form a trans-bidentate coordination to a metal atom.
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