I was reading Jan's answer to the following question-: Why can NCl3 be hydrolyzed but CCl4 cannot?.
Since nitrogen is less electronegative than fluorine in $\ce{NF3}$, the electrophilic site is the Nitrogen atom. That means the water molecule should attack nitrogen atom in an $\mathrm{S_N2}$ manner. The stearic crowding around the atom is also less. Then why is the reaction not taking place? Is it only because fluoride ion is a poor leaving group due to its high basic strength?

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    $\begingroup$ I would assume that thermodynamic factors need consideration here too, NF3 is relatively stable and has a negative enthalpy of formation. $\endgroup$ – AS_1000 Aug 22 '17 at 11:00
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    $\begingroup$ Bonds of other second period elements to fluorine are relatively strong. So in addition to the other factors already mentioned, there is an inherent high activation energy. Fluoroalkanes are not good substrates for nucleophilic substitution either, same reason. $\endgroup$ – Oscar Lanzi Aug 22 '17 at 12:51
  • $\begingroup$ Can anyone summarise everything into an answer with data and examples if possible? $\endgroup$ – Kartikeya Badola Aug 22 '17 at 14:30
  • $\begingroup$ @KartikeyaBadola They aren't related. $\endgroup$ – Mithoron Aug 22 '17 at 15:31

Nitrogen trifluoride is extremely inert to hydrolysis, attack by base or acids or oxidation because of the fact that there is no d-orbitals in Nitrogen trifluoride and fluorine is far more electronegative than nitrogen. However, in the presence of base or acids, nitrogen trifluoride can however undergo hydrolysis because there is now excess of nucleophile which can attack nitrogen trifluoride.

There is a old paper which discuss the hydrolysis of nitrogen trifluoride in presence of acids and base.

In the presence of aqueous base, however, slow hydrolysis occurs at 100°C yielding nitrite and fluoride.

$$\ce{NF3 + 4 OH- ->[100℃] NO2- + 3F- + 2H2O}$$

It further says:

This behavior differs sharply from that of nitrogen trichloride, which is known to give ammonia and hypochlorite under similar con- ditions. The latter products are readily explained in terms of nucleophilic attack directed at the chlorine atoms, a mechanism which appears reasonable in view of the fact that the electronegativities of $\ce{N}$ and $\ce{Cl}$ are very nearly the same and that the halogen may easily expand its valence shell. Obviously, these considerations cannot be applied to the nitrogen trifluoride molecule since fluorine is considerably more electronegative than nitrogen and it has no available d orbitals. Although the nitrogen atom also has no free orbitals, the relatively low electron density would at least offer less resistance to the approach of a nucleophile .

enter image description here

The proposed intermediate $\ce{HONF2}$ would be expected to be unstable with respect to the loss of $\ce{HF}$, as is apparently the case with the unknown perfluoro alcohols .

Two other reaction modes worth considering include the formation of an intermediate activated complex with water.

enter image description here

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    $\begingroup$ Find a paper that isn't outdated. $\endgroup$ – Mithoron Aug 24 '17 at 14:02
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    $\begingroup$ @Mithoron At least that paper tells us that $\ce{NF3}$ hydrolyses at $\pu{100 ^\circ C}$ in highly basic conditions. In reverse, that means hydrolysis is probably kinetically inhibited at room temperate. And it also states that it does indeed follow the expected $\mathrm{S_N2}$ mechanism with nucleophilic attack on nitrogen followed by displacement of the fluoride. (I reserve the right to be skeptical about the $\ce{HF}$ dissociation but it’s not entirely unlikely.) $\endgroup$ – Jan Aug 24 '17 at 15:39
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    $\begingroup$ @Mithoron Why? Did chemistry changed from the 40s ? $\endgroup$ – permeakra Aug 24 '17 at 17:19
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    $\begingroup$ @permeakra Any explanation with "having d-orbitals" is outdated. $\endgroup$ – Mithoron Oct 7 '17 at 23:53

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