Intrinsic acid-base properties of molecules. Binding energies of lithium(1+) ion to .pi.- and n-donor bases

Staley, Ralph H.; Beauchamp, J. L.

doi:10.1021/ja00853a050

Cited by 205 publications

(102 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…However the affinity of DMF for Li (50 kcal mol À1 ) has never been measured directly, but is the conjunction of an affinity of 34 kcal mol À1 of H 2 O and several equilibrium measurements of the type described by reaction (1). [24] Since this is a fairly (1) indirect determination, the experimental error bar is difficult to evaluate but might be expected to be large. We have therefore computed DMF and DMF ± Li at the MP2/basis2// MP2/basis1 level (including BSSE at the MP2/basis2 level) in order to obtain an improved affinity of DMF for Li .…”

Section: Isomermentioning

confidence: 99%

Interaction of Alkali Metal Cations (Li+-Cs+) with Glycine in the Gas Phase: A Theoretical Study

Hoyau¹,

Ohanessian²

1998

Chem. Eur. J.

177

246

View full text Add to dashboard Cite

The complexes formed by alkali metal cations (Cat ) and glycine (Gly) were studied by means of ab initio quantum chemical methods. Seven types of Gly ± Cat interaction were considered in each case. It was found that in the most stable forms of Gly ± Li and Gly ± Na the metal ion is chelated between the carbonyl oxygen and nitrogen ends of glycine. For Gly ± K an isomer involving complexation with both oxygens of the carboxylic function is found to be degenerate with the above chelate, and becomes slightly more stable for Gly ± Rb and Gly ± Cs. In all cases, interaction of the ion with the carboxylate group of zwitterionic glycine is also low in energy. Computed binding energies (DH 298 , kcal mol À1

show abstract

Section: Isomermentioning

confidence: 99%

Interaction of Alkali Metal Cations (Li+-Cs+) with Glycine in the Gas Phase: A Theoretical Study

Hoyau¹,

Ohanessian²

1998

Chem. Eur. J.

177

246

View full text Add to dashboard Cite

show abstract

“…However, (C3H,),S is well off the line, signifying a much stronger relative interaction with CH3Hg+ than for the nitrogen bases. This is in contrast to the much weakened basicity (enthalpy of binding) of (CH3),S compared with (CH3),0 or (CH3),N for Li+ relative to that for H+ (15). An increased covalent character relative to both H+ and Li+ of the binding of the larger CH3Hg+ to the more polarizable second row element is indicated.…”

Section: Resultsmentioning

confidence: 73%

Relative methylmercury cation affinities in the gas phase determined by high pressure mass spectrometry

Stone¹,

Splinter²

1981

Can. J. Chem.

View full text Add to dashboard Cite

. Can. J. Chem. 59, 1779Chem. 59, (1981. A pulsed electron beam, high pressure mass spectrometer has been used to determine equilibrium constants for the exchange of CH,Hg+ between bases; CH3Hg.Bl+ + B2 * CH3Hg.B2+ + B,. A series of aromatic, hydrocarbon bases has been studied at 417 K and several nitrogen bases have been studied at 580 K. There is a good linear correlation between differences in CH,Hg+ affinity (AGO) and H+ affinity for bases in each series. The single sulfur base examined ((C3H7),S) shows anomalously high relative affinity for CH,Hg+ compared with H+ while two oxygen bases (CH,COOCH, and C6H,N02) show lesser relative affinity. These results are in qualitative agreement with the hard-soft acid base theory. AHo and ASo values have been obtained from Arrhenius plots. For a pair of aromatic bases (toluene-ethylbenzene) AHo is of the same magnitude as that for H+ and ASo may be calculated using partition functions for translation and external rotation. For toluene/methylacetate the difference in binding energy is much greater for H+ than for CH,Hg+ and a similar calculation of ASo gives a result not consistent with the expenmental value.

show abstract

“…Since this reaction enthalpy is measured to be Ϫ37 ± 2 kcal/mol applying ion cyclotron resonance technique [7] it is a unique chance to calibrate the ab initio calculations. The expected C 6v species exhibits an LiϪC bond of 239.1 pm and a CϪC bond of 140.6 pm which is slightly longer than in free benzene (139.6 pm).…”

Section: Resultsmentioning

confidence: 99%

Carbonyl and Benzene Complexes of Lithium: Transition-Metal-Like Behaviour of Lithium in Organolithium Compounds

Tacke¹

1998

Eur. J. Inorg. Chem.

View full text Add to dashboard Cite

Intrinsic acid-base properties of molecules. Binding energies of lithium(1+) ion to .pi.- and n-donor bases

Cited by 205 publications

References 0 publications

Interaction of Alkali Metal Cations (Li+-Cs+) with Glycine in the Gas Phase: A Theoretical Study

Interaction of Alkali Metal Cations (Li+-Cs+) with Glycine in the Gas Phase: A Theoretical Study

Relative methylmercury cation affinities in the gas phase determined by high pressure mass spectrometry

Carbonyl and Benzene Complexes of Lithium: Transition-Metal-Like Behaviour of Lithium in Organolithium Compounds

Contact Info

Product

Resources

About