Question

Ligand dissociation for PdL4 is only slight when L = P(OMe3), yet when L = PPh3...

Ligand dissociation for PdL4 is only slight when L = P(OMe3), yet when L = PPh3
the dissociation is fairly complete. Explain the reason why this might be the case if
the cone angle is not relevant for this example (cone angles with 10 degrees of each
other). Hint: Think about the orbitals of P-R when R is more electronegative.

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Answer #1

Besides ligand cone angle the dissociation of phosphine ligand is also depends upon electronic factors. The electron withdrawing group presents in phosphine like pph3 renders the phosphine ligand a weaker donor resulting the weaker Pd-P bond relative to the OMe group which is electron donating in nature . Due to weak Pd-P bond in pd-PPh3 the ligand dissociation takes place faster than the pd-P(OMe)3.

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