Stereochemical consequences of ionic bonding in alkali metal acetylacetonates

Raban, Morton; Noe, Eric A.; Yamamoto, Gaku

doi:10.1021/ja00462a010

Cited by 41 publications

(23 citation statements)

References 3 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The anions 1-X gave rise to a single set of NMR signals in [D 6 ]DMSO solution, except for (1-COMe)ÀK, which shows two sets of broad signals in the ratio 1:1.3. For this anion, four possible configurations have to be considered (Scheme 3).…”

Section: Resultsmentioning

confidence: 99%

Quantification of Ion‐Pairing Effects on the Nucleophilic Reactivities of Benzoyl‐ and Phenyl‐Substituted Carbanions in Dimethylsulfoxide

Corral-Bautista

Appel

Frickel

et al. 2014

Chemistry A European J

View full text Add to dashboard Cite

Second-order rate constants for the reactions of acceptor-substituted phenacyl (PhCOCH(-) Acc) and benzyl anions (PhCH(-) Acc) with diarylcarbenium ions and quinone methides (reference electrophiles) have been determined in dimethylsulfoxide (DMSO) solution at 20 °C. By studying the kinetics in the presence of variable concentrations of potassium, sodium and lithium salts (up to 10(-2) mol L(-1) ), the influence of ion-pairing on the reaction rates was examined. As the concentration of K(+) did not have any influence on the rate constants at carbanion concentrations in the range of 10(-4) -10(-3) mol L(-1) , the acquired rate constants could be assigned to the reactivities of the free carbanions. The counter ion effects increase, however, in the series K(+)

show abstract

Section: Resultsmentioning

confidence: 99%

Quantification of Ion‐Pairing Effects on the Nucleophilic Reactivities of Benzoyl‐ and Phenyl‐Substituted Carbanions in Dimethylsulfoxide

Corral-Bautista

Appel

Frickel

et al. 2014

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…Analysis of the NMR spectra shows that ortho-hydroxybenzaldehydes remind b-diketones [5][6][7]: there is no qualitative difference in chelation of the lithium, sodium and potassium cations in their O-alkali metal derivatives. …”

Section: Resultsmentioning

confidence: 99%

“…formation of the hydrogen bond between the acidic hydrogen and electronegative atoms. For the same reason the sp 2 hybridized lithium atom in the respective enolates of b-dicarbonyl compounds interacts with the carbonyl oxygen atom [4][5][6][7]. Since the size of p orbital of the sp 2 hybridized Na and K atoms precludes its effective overlapping with the p orbital of the carbonyl oxygen atom, formation of the six-membered quasi-rings in the molecules of the sodium and potassium enolates of b-diketones seems impossible.…”

Section: Introductionmentioning

confidence: 99%

“…So far no p-electron delocalization in the quasi-ring of salicylaldehyde and its O-alkali metal derivatives (Scheme 2, Y = O, X = Li, Na, K) have been studied. There is no qualitative difference in chelation of the sodium and potassium cations in the respective derivatives of b-diketones [5][6][7]. This effect was found to be the most and less strong in the lithium and potassium enolates, respectively [5].…”

Section: Introductionmentioning

confidence: 99%

“…There is no qualitative difference in chelation of the sodium and potassium cations in the respective derivatives of b-diketones [5][6][7]. This effect was found to be the most and less strong in the lithium and potassium enolates, respectively [5]. The NMR spectra of lithium, sodium, and potassium derivatives are believed to be affected by the size of the cation and degree of the salt dissociation [4].…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations