Why are there more fluoride compounds formed with Xenon?

Based on WebElements, of the Noble Gases, $\ce{He}$ and $\ce{Ne}$ do not react with any of the halogens; however:

• $\ce{HArF}$ has been detected at low temperatures (thank you to @bon and @Martin in the comments)
• $\ce{KrF2}$ can be synthesised at low temperatures.
• Xenon can react with fluorine to produce $\ce{XeF2}$, $\ce{XeF4}$ and $\ce{XeF6}$
• Radon can react with fluorine to produce $\ce{RnF2}$

I understand that fluorine is the only halogen that seems to react with the Noble Gases (partly due to the related question Why Aren't Chlorides Of The Noble Gases As Prevalent As Their Fluorides?. My question is

Why are there more fluoride compounds formed with Xenon compared to the other Noble Gases?

• Do you know the three-center four-elcetron bound ? – ParaH2 May 22 '15 at 16:12
• Also $\ce{HArF}$ has been detected at very low temperatures and confirmed to have proper bonds between the atoms. – bon May 22 '15 at 17:24
• Calculations for HArF show that there is a covalent HAr and an ionic ArF interaction: nature.com/nature/journal/v406/n6798/full/406836a0.html – Martin - マーチン Jun 30 '15 at 13:38
• Thank you @bon and Martin, I have added this compound into the question – user15489 Jun 30 '15 at 13:55

The reason that we discovered more fluorides of Xeon than Helium, Argon, and Krypton is quite obvious and you might already know it. As lighter noble gases have more stable shell configuration, it is more difficult to make any kind of compound, including fluorides.

Also, the higher amount of fluorine atoms in a molecule of the compounds means drawing more electron from the noble gas, which is thermodynamically not preferred. Thus, KrF4 and KrF6 are far less stable than KrF2. The quantum chemical calculation confirmed this. (Dixon 2007) The same reference said that they are stable, but have not been synthesized yet, and the synthesis would be very difficult.

For Radon it is a different problem. Briefly, there might be more fluoride compounds of Radon than Xenon, but the synthesis is difficult to be confirmed.

Even though Radon is less inert than Xenon and its compounds were predicted and calculated to be more chemically stable than Xenon compounds (Chernick 1962, Thayer 2005), it is difficult to study. Radon is is rare and radioactive (half-life of 3.8 days). Studying chemical compounds in trace amount is a difficult task. There are claims for discoveries of RnF4 and RnF6 (also in the above references), but confirming that you have synthesized new compounds in trace amount is extremely difficult because the evidence is not obvious. RnF8 was calculated to be unstable, but should be more possible than XeF8

References:

1 Dixon et al. Heats of formation of krypton fluorides and stability predictions for KrF4 and KrF6 from high level electronic structure calculations. Inorganic Chemistry 2007 46 (23), 10016-10021

2 Chernick et al. Fluorine Compounds of Xenon and Radon. Science 1962 138 (3537), 136-138.

3 Thayer. Relativistic Effects and the Chemistry of the Heaviest Main-Group Elements. Journal of Chemical Education 2005 82 (11), 1721

• Another reason why the fluorides of the lighter noble gasses are less stable is, that the elements are smaller, which leads to a smaller fluorine-fluorine distances and higher repulsion between the non-bonding electrons (Pauli repulsion). – Martin - マーチン Jun 30 '15 at 13:35