Determination of Equilibrium Constants of Silver-Olefin Complexes Using Gas Chromatography

Contributions to the theory and practice of the chromatographic separation of enantiomers

“…23 The concept of the retention-increment RV (formerly called retention-increase 23 ) is an extension of an approach to determine complexation constants in argentation GC. 11 Its principle is depicted in Figure 4.…”

“…9,10 The p-complexation ability of silver(I) ions toward olefins utilized for selective separations of alkene mixtures by argentation gas chromatography was already well established at the beginning of the 1960s. 11,12 Unfortunately, the use of transition metal complexes containing optically active phosphines and phosphites as chiral selectors in GC failed despite their versatility in transition-metal-mediated asymmetric catalysis. Consequently, the work of Feibush et al 13 was adopted in utilizing chiral camphor-derived b-diketonate anions as ligands for metal ions not only for the use as paramagnetic chiral NMR shift reagents (ref.…”

Magnetic resonance studies of metal–olefin complexes. I. Electron spin resonance spectra of γ-irradiated silver perchlorate cycloalkene complexes

“…Studies of the relative stability of silver-olefin complexes (7,8) reveal the order of increasing stability to be: bicycloolefins > endocyclo-monoolefins > aliphatic olefins. Traynham and Olechowski (8) attribute this to the effect of ring strain upon the n: basicity of the olefins and thus upon the strength of the coordinate bond.…”

The Structure-Stability Relationship of the Metal Ion Complexes of Unsaturated Compounds. V. Stabilities of the Silver-Ion Complexes of Some cis-Stable Olefins

“…The different abilities of geometrical isomers in forming complexes with the silver ion have already been reported for several alkenes1d, 5,6) and alkenyl alkyl ethers.9) In all these cases, the cis isomers have greater equilibrium constants than the corresponding trans isomers, as shown in Table 2 (4 and 5). Such effects of the geometrical isomerism on the stabilities of the complexes have been interpreted in terms of strain effects.…”