Paramagnetic alkali-aromatic ion-pair structures. The crystal structure of bis[1,2-bis(2-methoxyethoxy)ethane]sodium biphenylide

Noordik, J. H.; Beurskens, P. T.; Hark, T. E. M. van den; Smits, J.M.

doi:10.1107/s0567740879004295

Cited by 19 publications

(10 citation statements)

References 7 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Crystallization kinetics for this phase are slow, however, even when n ≤ 2. As yet, there are no known crystal structures for (G3) 2 :LiX solvates, but (G3) 2 :NaX solvates are SSIPs with all eight EOs coordinated to the Na + cations. − It is possible for all four EOs of a G3 molecule to coordinate a single Li + cation in a crown ether-like conformation . The (G3) 2 :LiX solvates, therefore, probably resemble (12-crown-4) 2 :LiX solvates such as (12-crown-4) 2 :LiTFSI .…”

Section: Resultsmentioning

confidence: 99%

Glyme−Lithium Salt Phase Behavior

2006

View full text Add to dashboard Cite

Phase diagrams are reported for glyme mixtures with simple lithium salts. The glymes studied include monoglyme (DME), diglyme, triglyme, and tetraglyme. The lithium salts include LiBETI, LiAsF6, LiI, LiClO4, LiBF4, LiCF3SO3, LiBr, LiNO3, and LiCF3CO2. The phase diagrams clearly illustrate how solvate formation and thermophysical properties are dictated by the ionic association strength of the salt (i.e., the properties of the anions) and chain length of the solvating molecules. This information provides critical predictive capabilities for solvate formation and ionic interactions common in organometallic reagents and battery electrolytes.

show abstract

Section: Resultsmentioning

confidence: 99%

Glyme−Lithium Salt Phase Behavior

2006

View full text Add to dashboard Cite

show abstract

“…Recently we succeeded in solving the crystal structure of NaBp.2Tg. A full account of the structure determination of this compound will be given elsewhere (11). Table 1 gives the single crystal data of NaBp.2Tg along with those of KBp.2Ttg and RbBp.2Ttg for comparison purposes, (12).…”

Section: Structure Determinationsmentioning

confidence: 99%

Structure of alkali biphenyl ion pairs in solution and in the solid state

Boer¹,

Klaassen²,

Mooij³

et al. 1979

Pure and Applied Chemistry

Self Cite

View full text Add to dashboard Cite

NMR experiments on sodium biphenyl (NaBp), potassium biphenyl (KBp) and ribidium biphenyl (RbBp), dissolved in various solvents are summarized with emphasis on the structural information which can be obtained from such experiments. The crystal structures of NaBp.2Tg (Tg = triglyme), KBp.2Ttg and RbBp.2Ttg (Ttg tetraglyme) are discussed, in relation to the NMR results obtained for these systems in solution. In the solid state these crystals may be considered to be built up of solvent separated ion pairs. Magnetic experiments are reported for single crystals of the three systems. Susceptibility measurements revealed a ferromagnetic coupling in NaBp.2Tg and KBp.2Ttg and an antiferromagnetic coupling in RbBp.2Ttg. All crystals exhibit an exchange narrowed ESR line, with an orientation dependent linewidth. From the resonance positions the molecular g tensor of the biphenyl anion could be derived. The orientation dependent linewidth is due to dipolar interactions between the spins. A quantitative explanation of it could not be given at present.

show abstract

“…Therefore, it has only been possible to characterize most monomeric hydrocarbon radical cations by spectroscopic methods such as ESR and electronic absorption spectroscopy, and examples of structural characterization by X-ray crystallography are quite rare. This limitation is in sharp contrast to the numerous examples of successful isolation and X-ray structural determination of various aromatic hydrocarbon radical anions, dianions, a radical trianion, and even a tetraanion . Thus, the synthesis and isolation of stable aromatic hydrocarbon radical cations and the elucidation of their structures still remain as an important issue in organic chemistry.…”

Section: Introductionmentioning

confidence: 97%

Structural Studies on the Radical Cations of Benzene, Naphthalene, Biphenylene, and Anthracene Fully Annelated with Bicyclo[2.2.2]octene Frameworks

2000

View full text Add to dashboard Cite

The cyclic voltammetry of benzene 1, naphthalene 2, biphenylene 3, and anthracene 4 fully annelated with bicyclo[2.2.2]octene showed that their cationic species have enhanced kinetic and thermodynamic stability as compared with the corresponding polymethyl analogues. Chemical one-electron oxidation of these neutral aromatic hydrocarbons led to facile isolation of their radical cation salts, which are persistent at ambient temperature even in air, and allowed X-ray crystallographic determination of their structures for the first time for the monomer radical cations of alkyl-substituted benzene, naphthalene, and biphenylene. The π-systems of these radical cations are planar except for that of the naphthalene radical cation 2 •+. The structure of the benzene ring of 1 •+ precludes the observation of a static Jahn−Teller distortion in the crystal at −100 °C. For the radical cations of 2−4, the geometrical changes in π-systems upon one-electron oxidation are consistent with what can be predicted from the orbital coefficients of the HOMO of the neutral molecules. Characteristic changes in the lengths of the σ-bonds of the bicyclic framework involved in σ−π conjugation (C−C hyperconjugation) were also observed. Theoretical calculations, using ab initio molecular orbital (HF/6-31G*) and density functional (B3LYP/6-31G*) methods, have been used to interpret the experimental data.

show abstract

Paramagnetic alkali-aromatic ion-pair structures. The crystal structure of bis[1,2-bis(2-methoxyethoxy)ethane]sodium biphenylide

Abstract: Abstract[Na (CsH 1804) The biphenyl anion is significantly non-planar. The local symmetry of the sodium-triglyme part of the structure is close to twofold and nearly 222.

Cited by 19 publications

References 7 publications

Glyme−Lithium Salt Phase Behavior

Glyme−Lithium Salt Phase Behavior

Structure of alkali biphenyl ion pairs in solution and in the solid state

Structural Studies on the Radical Cations of Benzene, Naphthalene, Biphenylene, and Anthracene Fully Annelated with Bicyclo[2.2.2]octene Frameworks

Contact Info

Product

Resources

About