In some occasions, if the ligand acts on Pd it do so as a monodentate ligand. I am attempting to explain this phenomenon but came into a block.

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    $\begingroup$ I believe there must be cases when it works with NH2 end alone, just not on Pd. Long story short, think of HSAB theory. $\endgroup$ – Ivan Neretin Jun 20 '19 at 10:34

So basically, you're comparing a soft base and a hard base. In HSAB theory, a soft acid like Pd2+, would preferably react with a soft base like R-PH2. Soft acids and bases are easily polarized because of their size. Although, the possibility of the ligand acting as a bidentate can't be ignored, the P to Pd2+ interaction is thermodynamically favored than N to Pd2+ interaction.


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