Page 324 - Arrow Pushing in Inorganic Chemistry A Logical Approach to the Chemistry of the Main Group Elements

THE NOBLE GASES
304
As in many ligand exchange reactions, the mechanism involves the formation of a bridged
intermediate, in this case involving a P–O–Xe bridge:
F
+ −
P O F F
F
F F F − F
F Xe Xe (8.11)
F F + F F
F F P F
F
F
A fluoride migration may then take place. A second fluoride migration, concomitant with
P–O bond cleavage, may then provide a possible route to the final products:
F
F F
F
− F F
O Xe O Xe
+ F
F P F F F P F F
F
F F
F F (8.12)
−
F F F O
F O Xe F F F
F P F + Xe
P +
F F F F F
F F F
F

REVIEW PROBLEM 8.3
−
XeF reacts with nitrate (NO ) to give nitryl fluoride (NO F) and XeOF :
6 3 2 4
− −
XeF + NO → NO F + XeOF + F
6 3 2 4
Suggest a mechanism.

+
8.3 XENON FLUORIDES AS F DONORS AND OXIDANTS
A perusal of standard reduction potentials (see, e.g., Table 1.6) immediately shows that
XeF is a powerful oxidant. Thus, it readily oxidizes HCl to Cl :
2 2
XeF + 2HCl → Xe + HF + Cl 2 (8.13)
2
Given that HF is a product and that it has a very high bond dissociation energy (BDE
569 kJ/mol), it’s reasonable to start by protonating one of fluorines of XeF .
2
H
+ −
H CI (8.14)
F Xe F F Xe F + CI