Electron Donor-Acceptor Interactions of Molecular Iodine with Olefins

Gas chromatographic study of interactions between aliphatic amines and metallic ions

“…It is generally accepted that the coordinating capacity follows the decreasing sequence NHs > NH2R > NHR2 > NR3. Hatfield and Yoke's (7) findings from the stoichiometry of the complexes formed by condensation of ethyl-, diethylor triethylamine on cobalt, zinc, and calcium halides, agree with this order. Drago et al (2) were able to precipitate from methanol, Ni(II) complexes with six molecules of primary monoamine, but not with secondary or tertiary amines; energies of the nickel-ligand bonds for the complexes they obtained, decrease the longer the hydrocarbon chain.…”

Kinetic evidence for complex formation in alkene bromination

“…In this technique, a pair of alkenes is treated with a limiting amount of bromine and the relative amounts of each alkene that react at infinite dilution of bromine should be equal to the ratio of the rate constants. For the bromination reactions, the relationship derived from eq 2 can be expressed by eq 19, where k and k' are the apparent rate dA k dD " V (19) constants for alkenes A and D, respectively, and the alkenes are present in an equimolar ratio. Equation 19 implicitly assumes that no complexation is involved in the reaction and relative reactivity ratio would be the same whether determined by a competitive technique or by a ratio of actual kinetic rate constants.…”

The Stereochemistry of Electrophilic Additions to Olefins and Acetylenes

“…Iodine and iodine chloride are known to form complexes with olefins and other unsaturated hydrocarbons (247)(248)(249) and iodination of olefins and acetylenes in solution can occur by either ionic or radical pathways (250)(251)(252)(253)(254)(255). The addition of iodine to ethylene (256) or acetylene (257) is exothermic by only about 10 kcal.…”