[Jzalkm]

looking for the mechanism of oxidation of phosphorus compound e.g PR3 using manganese (IV) oxide.
organic reaction

[Jzalkm]

stuck at the beginning. any help will be appreciated.

[discodermolide]

stuck at the beginning. any help will be appreciated.

Attack pf the P atom at the Mn center, pushing the electrons to an oxygen atom, making it negative and the P positive. The negative oxygen attacks the P+ breaking the P-Mn bond. The lone pair of the second oxygen moves into the Mn atom to give a Mn-O triple bond with further movement of electrons toward the P atone generating a P=O bond.
Sorry I can draw it but don't know how to post it here.

[Jzalkm]

thanks.
i have tried translate the wordings into picture. kindly confirm.

hint to upload picture: click additional options and attach picture.

[discodermolide]

thanks.
i have tried translate the wordings into picture. kindly confirm.

hint to upload picture: click additional options and attach picture.

Well translated, one thing it should be a Mn triple bond to oxygen in the final Mn product.

[Jzalkm]

the triple bond did not understand.

appended it. that was great help, thanks a lot.

[nox]

One thing I think I should point out: often times with TM oxidants, the reaction may go through a radical rather than polar mechanism.

I don't know anything about this oxidation in particular, but I really dislike the 3-membered intermediate, and the triple bonded MnO seems a bit ridiculous.

[discodermolide]

One thing I think I should point out: often times with TM oxidants, the reaction may go through a radical rather than polar mechanism.

I don't know anything about this oxidation in particular, but I really dislike the 3-membered intermediate, and the triple bonded MnO seems a bit ridiculous.

Instead of criticizing suggest something else!

[AWK]

thanks.
i have tried translate the wordings into picture. kindly confirm.

hint to upload picture: click additional options and attach picture.

Well translated, one thing it should be a Mn triple bond to oxygen in the final Mn product.

Triple bond in MnO is an evident error

[Jzalkm]

MnO is ionic?
the "by-product" is?

the three member ring i think is ok

[AWK]

All polymorphs of MnO2 shows MnO6 octahedra in their crystal structures, so I suggest the mechanism analogous to oxidation of gem-diols by permanganate through four-membered transition state. From stoichiometric point of view MnO or Mn₂O₃ can be formed depending on amount of MnO₂ used.

[Jzalkm]

point noted.
will the reaction of interest involve 1 mol of each reactants?

oxidation of geminal diols involve two OH groups.

[AWK]

oxidation of geminal diols involve two OH groups.

and five-membered transition state

[nox]

One thing I think I should point out: often times with TM oxidants, the reaction may go through a radical rather than polar mechanism.

I don't know anything about this oxidation in particular, but I really dislike the 3-membered intermediate, and the triple bonded MnO seems a bit ridiculous.

Instead of criticizing suggest something else!

Sorry if my post came across as rude, I did not intend to criticize.