Trimethylperoxonium Ion, CH3OO(CH3)2+ 1

Oláh, George A.; Rasul, Golam; Burrichter, Arwed; Hachoumy, Mohammed; Prakash, G. K. Surya; Wagner, A.

doi:10.1021/ja9715511

Cited by 13 publications

(15 citation statements)

References 12 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…also observed for the unsubstituted guanidinium ion [C(NH 2 ) 3 ] + . 19 These 4-ppm deshieldings in DMSO, compared with H 2 O, are likely caused by the extremely strong H-bonding between guanidinium ion and DMSO. Partial proton transfer of the solute to a solvent that acts as such a strong H-bond acceptor is estimated to be 10-30%.…”

Section: Discussionmentioning

confidence: 99%

Modeling Amino Acid Side Chains in Proteins: ¹⁵N NMR Spectra of Guanidino Groups in Nonpolar Environments

Xiao

Braiman

2005

J. Phys. Chem. B

View full text Add to dashboard Cite

Natural-abundance 15N NMR spectroscopy on dodecylguanidine reveals solvent and protonation effects that model those that could occur for the arginine side chain in proteins. Our results demonstrate that the 15N chemical shifts of the terminal guanine nitrogens strongly depend on the solvent chosen for measurements. A polar H-bond-donating solvent like water has strongly deshielding effects on the neutral guanidine group (with the latter acting predominantly as an H-bond acceptor). As a result, a substantial upfield shift occurs when neutral guanidine is dissolved instead in a non-H-bonding solvent (chloroform). These solvent effects can be as large as those induced by protonation changes. This limits the ability of 15N chemical shifts to distinguish the protonation state of the arginine side chain, at least without specific knowledge of its environment. These results help to reconcile previous interpretations about the protonation state arg-82 in the M state of bacteriorhodopsin based on FTIR and 15N NMR spectroscopy. That is, contrary to earlier conclusions from solid-state NMR, the side chain of arg-82 could undergo a deprotonation between the bR and M states, but only if it also experienced a significant decrease in the H-bonding character and polarity of its environment. In fact, the average 15N chemical shift of the two Neta of arg-82 in bacteriorhodopsin's M intermediate (from the previous NMR measurements) is 17 ppm upfield from the corresponding value for the deprotonated arginine side chain in aqueous solution at pH >14, but only 3 ppm upfield from the value for deprotonated dodecylguanidine in chloroform.

show abstract

Section: Discussionmentioning

confidence: 99%

Modeling Amino Acid Side Chains in Proteins: ¹⁵N NMR Spectra of Guanidino Groups in Nonpolar Environments

Xiao

Braiman

2005

J. Phys. Chem. B

View full text Add to dashboard Cite

show abstract

“…This is paper 52 in the series ''Onium Ions''; paper 51 is ref. 23. Support of our work by the National Science Foundation and the Office of Naval Research is gratefully acknowledged.…”

Section: Fig 1 Calculated Structures Of 1-4 (Calculated Nbo Charges)mentioning

confidence: 93%

Helionitronium trication (NO ₂ He ³⁺ ) and helionitrosonium trication (HeNO ³⁺ )

Oláh¹,

Prakash²,

Rasul³

1999

Proc. Natl. Acad. Sci. U.S.A.

Self Cite

View full text Add to dashboard Cite

The structures and stabilities of helionitronium trication NO 2 He 3؉ and helionitrosonium trication HeNO 3؉ were calculated at the ab initio MP2͞6-31G** level. The C s symmetry structure was found to be a minimum for the NO 2 He 3؉ trication, which is isoelectronic and isostructural with the previously studied NO 2 H 2؉ . Dissociation of the C s symmetry structure into NO ؉ and OHe 2؉ is thermodynamically preferred by 183.1 kcal͞mol (1 cal ‫؍‬ 4.18 J), although a kinetic barrier of 12.4 kcal͞mol has to be overcome. The C ؕv symmetry structure was also found to be a minimum for the HeNO 3؉ trication.

show abstract

“…Triorganylperoxonium ions [R 2 OOR] ϩ , [13] -disulfonium ions [R 2 SSR] ϩ , [14,15] related organoselenium cations such as [(MeSe) 2 SeMe] ϩ [15] and [Ph 2 Se 6 ] 2ϩ [16] and oxytelluronium cations [R 2 TeOTeR 2 ] 2ϩ , [17,18] are well-known species; corresponding selenotelluronium salts [R 2 TeSeRЈ] ϩ X Ϫ , however, have not yet been reported in the literature, [5,12] Such compounds will undergo reductive elimination when the counterion X Ϫ is a good nucleophile towards the RЈSe ϩ group. Salts of the type [RRЈTeTeRЈ] ϩ X Ϫ have been proposed as reactive intermediates when dialkyl ditellurides were activated by alkyl halides for one-pot reactions with carbon nucleophiles.…”

Section: Reactionsmentioning

confidence: 99%

“…77 Se-and 125 Te-NMR spectra of the reaction mixture, however, did not provide evidence for the presence of the compound Mes 2 Te(SeC 6 F 5 ) 2 . [13] To elucidate whether the failure of the desired oxidative addition of 1 to the diaryl telluride 2 was really due to thermal instability of Mes 2 Te(SeC 6 F 5 ) 2 (and not to kinetic factors), we then attempted to generate an [R 2 TeSeRЈ] ϩ cation by an independent route.…”

Section: Introductionmentioning

confidence: 99%

Novel Mesityltellurium Cations from Selenenation and Tellurenation Reactions of Dimesityl Telluride in the Presence of the Br2/AgSbF6 Reagent

Jeske

Mont

Ruthe

et al. 2000

Eur. J. Inorg. Chem.

View full text Add to dashboard Cite

Trimethylperoxonium Ion, CH₃OO(CH₃)₂⁺ ¹

Cited by 13 publications

References 12 publications

Modeling Amino Acid Side Chains in Proteins: ¹⁵N NMR Spectra of Guanidino Groups in Nonpolar Environments

Modeling Amino Acid Side Chains in Proteins: ¹⁵N NMR Spectra of Guanidino Groups in Nonpolar Environments

Helionitronium trication (NO ₂ He ³⁺ ) and helionitrosonium trication (HeNO ³⁺ )

Novel Mesityltellurium Cations from Selenenation and Tellurenation Reactions of Dimesityl Telluride in the Presence of the Br2/AgSbF6 Reagent

Contact Info

Product

Resources

About

Trimethylperoxonium Ion, CH3OO(CH3)2+ 1

Cited by 13 publications

References 12 publications

Modeling Amino Acid Side Chains in Proteins: 15N NMR Spectra of Guanidino Groups in Nonpolar Environments

Modeling Amino Acid Side Chains in Proteins: 15N NMR Spectra of Guanidino Groups in Nonpolar Environments

Helionitronium trication (NO 2 He 3+ ) and helionitrosonium trication (HeNO 3+ )

Novel Mesityltellurium Cations from Selenenation and Tellurenation Reactions of Dimesityl Telluride in the Presence of the Br2/AgSbF6 Reagent

Contact Info

Product

Resources

About

Trimethylperoxonium Ion, CH₃OO(CH₃)₂⁺ ¹

Modeling Amino Acid Side Chains in Proteins: ¹⁵N NMR Spectra of Guanidino Groups in Nonpolar Environments

Modeling Amino Acid Side Chains in Proteins: ¹⁵N NMR Spectra of Guanidino Groups in Nonpolar Environments

Helionitronium trication (NO ₂ He ³⁺ ) and helionitrosonium trication (HeNO ³⁺ )