Alkali Metal solutions Effect of Two Cyclic Polyethers on solubility and Spectra

Dye, James; Lok, Mei Tak; Tehan, Frederick J.; Coolen, Richard B.; Papadakis, Nicholas; Ceraso, Joseph M.; DeBacker, Marc G.

doi:10.1002/bbpc.19710750722

Cited by 41 publications

(11 citation statements)

References 23 publications

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“…[36] [37] Highly reactive solutions of [K(crypt-222)] + alkalides and electrides [38] in Et 2 O have been found 'stable for many hours at À80°C'. [39] 9 The acidity of toluenes is particularly sensitive to substituent effects. [45] 10 While no pK a data for CHF 3 has been reported in DMSO, the value of 26 has been obtained in DMF, [25] [26] another member of the family of aprotic dipolar solvents.…”

Section: Is There a Way To Discern Between 1 And 2?mentioning

confidence: 99%

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On the Structure of [K(crypt‐222)]⁺

Harlow¹,

Benet‐Buchholz

Miloserdov

et al. 2018

Helvetica Chimica Acta

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Due to disorder, [K(crypt‐222)]+ CF3− (1) is crystallographically indistinguishable from its isomer, a 1:1 fluoroform clathrate of deprotonated [K(crypt‐222)]+, [K(crypt‐222{‐H+})]·CHF3 (2). In our preceding publications, 1 was characterized on the basis of combined X‐ray diffraction, NMR, reactivity, labeling, acid‐base, and DFT studies. Herein we report that neither incorporation of deuterium nor any other transformation of [K(crypt‐222)]+ is observed in the presence of CD3OD/CD3OK at 70 °C or CD3S(O)CD2K/(D6)DMSO at 23 °C over hours and even days. Since fluoroform is easily and quickly deprotonated under such conditions, the demonstrated greater acidity of CHF3 relative to [K(crypt‐222)]+ provides additional evidence in favor of 1 and against 2. Likewise, crystal packing analysis and DFT calculations support 1, which has now been refined in the ultimately correct space group R32. Our previously drawn conclusions regarding [K(crypt‐222)]+ CF3− and the existence of a ‘naked’ trifluoromethyl anion in a condensed phase remain valid. The recent alternative refinement (Becker and Müller, Chem. Eur. J. 2017, 23, 7081 – 7086) of our raw diffraction data has been improperly performed in the wrong space group to yield a non‐charge‐balanced model [K(crypt‐222)]+·CHF3, which is hereby repudiated. Becker and Müller's attempts to resolve the charge balance issue have produced models that are inadequate from the perspective of both crystallography and chemistry.

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Section: Is There a Way To Discern Between 1 And 2?mentioning

confidence: 99%

“…45 . Highly reactive solutions of [K(crypt‐222)] + alkalides and electrides in Et 2 O have been found ‘stable for many hours at −80 °C’ …”

mentioning

confidence: 99%

On the Structure of [K(crypt‐222)]⁺

Harlow¹,

Benet‐Buchholz

Miloserdov

et al. 2018

Helvetica Chimica Acta

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“…(K+An-")2 + ROH -X K+AnH" + K+OR" + An (28) (30) R. M, Fuoss and C. A. Kraus, J. Amer, Chem. Soc., 55, 2387 (1933).…”

Section: Resultsmentioning

confidence: 99%

Effect of ion-clustering and dianion formation on the rate of protonation of anthracenide by alcohols and water in two ethereal solvents

Minnich¹,

Long²,

Ceraso³

et al. 1973

J. Am. Chem. Soc.

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Anthracenide radical anions were formed by the reaction of anthracene with potassium or sodium in tetrahydrofuran (THF) and in dimethoxyethane (DME). The rate of reaction of the radical anion with a series of alcohols and with water was followed spectrophotometrically by using a scanning stopped-flow apparatus. The reactions of K+An • -in both solvents and of Na+An• -in THF were essentially second order in (M+An•-) and of variable (0-1) order in the proton donor. The reactions of Na+An •-with ethanol and with water in DME were

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“…Some authors assumed the possibility of electron pairing resulting in the formation of diamagnetic dielectrons (e 2 = ) [2,15]. macrocyclic ligands (L) afforded to prepare high concentrated alkali metal solutions in aprotic solvents [16][17][18][19][20]. macrocyclic ligands (L) afforded to prepare high concentrated alkali metal solutions in aprotic solvents [16][17][18][19][20].…”

Section: Introductionmentioning

confidence: 99%