Page 319 - Arrow Pushing in Inorganic Chemistry A Logical Approach to the Chemistry of the Main Group Elements

FURTHER READING 299
2. The diatomic elements act as oxidants and as electrophiles. Halogen molecules cleave
readily via both heterolytic and homolytic pathways:
−
Nu −
Nu X + X
X X (7.1)
Δ
X + X
or h
3. The disproportionation of molecular halogens in alkaline solution provides an entry
into higher oxidation state halogen chemistry. Higher oxidation states of halogens are
typically stabilized by strongly electronegative ligands such as fluoride, oxide, and
hydroxide.
4. So-called hypofluorous acid, which is not significantly acidic, serves as a useful oxy-
gen atom transfer agent.
5. Numerous interhalogen compounds, as well as cations and anions, are known. Several
engage in halide/fluoride ion transfer reactions.
6. By virtue of their tendency to undergo reductive elimination, higher-valent
organoiodine compounds serve as important oxidants in organic chemistry.
7. Higher-valent organobromine compounds are emerging as exciting new reagents in
organic chemistry. More susceptible to reductive elimination, they are more reactive
analogs of related organoiodine compounds.

FURTHER READING

Balard, A. “Sur une substance particulière contenue dans l’eau de la mer (About a Particular Substance
Present in Sea Water),” Annales de Chimie et de Physique, 2nd series, 1826, 32, 337–381.
Weeks, M. E. “The Discovery of the Elements: XVII. The Halogen Family,” J. Chem. Educ. 1932, 9,
1915–1932.
Zhdankin, V. V., ed. Hypervalent Iodine Chemistry: Preparation, Structure, and Synthetic Applica-
tions of Polyvalent Iodine Compounds; John Wiley & Sons, Inc.: Hoboken, NJ, 2013; 480 pp. A
comprehensive, up-to-date set of reviews.
Stang, P. J.; Zhdankin, V. V. “Organic Polyvalent Iodine Compounds,” Chem. Rev. 1996, 96,
1123–1178. An earlier review.
Rozen, S. “Selective Reactions of Bromine Trifluoride in Organic Chemistry,” Adv. Synth. Catal.
2010, 352, 2691–2707.
3
Ochiai, M.; Miyamoto, K.; Hayashi, S.; Nakanishi, W. “Hypervalent N-sulfonylimino- -bromane:
Active Nitrenoid Species at Ambient Temperature Under Metal-Free Conditions,” Chem. Comm.
2010, 46, 511–521.