Alkali Metal Diphenylmethanides: Synthetic, Computational and Structural Studies

Alexander, Jacob S.; Allis, Damian G.; Teng, Weijie; Ruhlandt‐Senge, Karin

doi:10.1002/chem.200700763

Cited by 11 publications

(19 citation statements)

References 54 publications

(116 reference statements)

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“…As stated before, Li + , Na + , and K + ions have high affinities for 12-crown-4, 15-crown-5, and 18-crown-6 ethers, respectively . Complexation with a smaller ligand (for example, a Na + ion with 12-crown-4 ether) usually requires coordination by two equivalents of the ligands. − G3, G4, and G5 contain four, five, and six oxygen atoms, respectively; accordingly, G3–Na[TFSA] and G4–K[TFSA] mixtures tend to form complexes in 2:1 ratios. A similar result was seen in the binary mixture of G2 and Li[TFSA], which forms [Li(G2) 2 ][TFSA] .…”

Section: Resultsmentioning

confidence: 96%

Effect of Ionic Size on Solvate Stability of Glyme-Based Solvate Ionic Liquids

et al. 2015

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A series of binary mixtures composed of glymes (triglyme, G3; tetraglyme, G4; pentaglyme, G5) and alkali-metal bis(trifluoromethanesulfonyl)amide salts (M[TFSA]; M = Li, Na, and K) were prepared, and the correlation between the composition and solvate stability was systematically investigated. Their phase diagrams and Raman spectra suggested complexation of the glymes with M[TFSA] in 1:1 and/or 2:1 molar ratio(s). From isothermal stability measurements, it was found that the formation of structurally stable complexes in the solid state did not necessarily ensure their thermal stability in the liquid state, especially in the case of 2:1 complexes, where uncoordinating or highly exchangeable glyme ligands existed in the molten complexes. The phase-state-dependent Raman spectra also supported the presence of free glymes in certain liquid complexes. The effect of the electric field induced by the alkali-metal cations on the oxidative stability of certain glyme complexes was examined by linear sweep voltammetry and quantum chemical calculations. Although the actual oxidative stability of complexes did not necessarily reflect the calculated HOMO energy levels of the glymes, the strong electric field induced by the smaller M(+) cations and proper coordination structures impart high stability to the glyme complexes. The results of thermogravimetry of complexes with different M(+) cations revealed that a balance of competitive interactions of the M(+) ions with the glymes and [TFSA](-) anions predominates the thermal stability.

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Section: Resultsmentioning

confidence: 96%

Effect of Ionic Size on Solvate Stability of Glyme-Based Solvate Ionic Liquids

et al. 2015

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“…The nature of the central alkali metal affects the chemical shifts of MCH fragments in 1 H and 13 C{ 1 H} spectra which increase in the transition from lithium to potassium. The chemical shifts of the atoms of the central methanide fragment in both the 1 H and 13 C NMR spectra of 1 TMEDA , 2 THF , and 3 THF are shifted substantially upfield in comparison to the unsubstituted benzhydryl anion, which can be associated with the electron-donating effect of Me and NMe 2 groups incorporated into the Ph 2 CH scaffold. The LiCH benzhydryl proton in the 1 H NMR spectrum of 1 TMEDA exhibits very weak 7 Li–H coupling ( 2 J LiH = 1.4 Hz), while the appropriate carbon appears in the 13 C{ 1 H} spectrum as a quartet with resolved 7 Li–C coupling ( 1 J LiC = 4.9 Hz) due to splitting to one 7 Li (spin 3/2, 92.41%), while the 6 Li– 13 C splitting is hidden (see Figure S2 in the Supporting Information).…”

Section: Resultsmentioning

confidence: 97%

“…Despite the large number of silyl-substituted benzylic alkali-metal complexes, diphenyl methanido derivatives remain scarce, and to date only benzhydryl (Ph 2 CH – ) , and silyl-substituted (Ph 2 C(SiR 3 ) − ) complexes are known. Herein we report on the synthesis of new alkali-metal derivatives of 2,2′-methylenebis( N , N ,4-trimethylaniline) .…”

Section: Introductionmentioning

confidence: 99%

Alkali-Metal Alkyl Complexes with the Tridentate Benzhydryl Ligand [2,2′-(4-MeC₆H₄NMe₂)₂CH]⁻

et al. 2018

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A series of alkali-metal alkyl complexes containing a tridentate benzhydryl ligand, [2,2′-(4-MeC 6 H 4 NMe 2 ) 2 CH]Li(TMEDA) (1 TMEDA ), [2,2′-(4-MeC 6 H 4 NMe 2 ) 2 CH]Na(THF) 3 (2 THF ), {[2,2′-(4-MeC 6 H 4 NMe 2 ) 2 CH]K(THF} 2 (3 THF ), and [2,2′-(4-MeC 6 H 4 NMe 2 ) 2 C-(SiMe 3 )]K (5), were synthesized and structurally characterized. Smaller Li and Na ions form the monomeric complexes 1 TMEDA and 2 THF featuring η 4 -CCCN coordination of the [2,2′-(4-MeC 6 H 4 NMe 2 ) 2 CH] − ligand, while the larger K affords the dimeric complex 3 THF , in which two different types of metal−ligand bonding, μ-η 5 -pentadienyl-κ 2 -NN and μκ 3 -CNN:η 6 -arene are realized. Application of the Me 3 Si-substituited analogue [2,2′-(4-MeC 6 H 4 NMe 2 ) 2 C(SiMe 3 )] − leads to the formation of the 1D coordination polymer {[2,2′-(4-MeC 6 H 4 NMe 2 ) 2 C(SiMe 3 )]K} ∞ (5) with μ-η 3 :η 6 bridging coordination of the ligands to potassium ions.

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“…The diphenylmethanide anion can frequently display a “flip” conformational disorder (Scheme ), which may or may not involve a center of symmetry. ,, Surprisingly, this disorder can be observed in both separated and contact species, providing a rationale on the scarcity of solid-state data.…”

Section: Diphenylmethane Ligandmentioning

confidence: 99%

s-Block Organometallics: Analysis of Ion-Association and Noncovalent Interactions on Structure and Function in Benzyl-Based Compounds

Torvisco

Ruhlandt‐Senge

2011

Inorg. Chem.

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The organometallic chemistry of alkali and alkaline-earth metals has been marred by synthetic setbacks because of their high reactivity. Advances in their synthesis and a better understanding of the stabilization effects of ligands and coligands have resulted in the revolution of s-block organometallics. Among those, benzyl-based derivatives have played a key role in developing this chemistry because factors such as the ligand size, charge delocalization, and introduction of electronic parameters along with metal effects can be analyzed. This article will focus on s-block benzylates and di- and triphenylmethanide derivatives with specific emphasis on the factors that stabilize the highly reactive metal species.

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Alkali Metal Diphenylmethanides: Synthetic, Computational and Structural Studies

Cited by 11 publications

References 54 publications

Effect of Ionic Size on Solvate Stability of Glyme-Based Solvate Ionic Liquids

Effect of Ionic Size on Solvate Stability of Glyme-Based Solvate Ionic Liquids

Alkali-Metal Alkyl Complexes with the Tridentate Benzhydryl Ligand [2,2′-(4-MeC₆H₄NMe₂)₂CH]⁻

s-Block Organometallics: Analysis of Ion-Association and Noncovalent Interactions on Structure and Function in Benzyl-Based Compounds

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Alkali Metal Diphenylmethanides: Synthetic, Computational and Structural Studies

Cited by 11 publications

References 54 publications

Effect of Ionic Size on Solvate Stability of Glyme-Based Solvate Ionic Liquids

Effect of Ionic Size on Solvate Stability of Glyme-Based Solvate Ionic Liquids

Alkali-Metal Alkyl Complexes with the Tridentate Benzhydryl Ligand [2,2′-(4-MeC6H4NMe2)2CH]−

s-Block Organometallics: Analysis of Ion-Association and Noncovalent Interactions on Structure and Function in Benzyl-Based Compounds

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Alkali-Metal Alkyl Complexes with the Tridentate Benzhydryl Ligand [2,2′-(4-MeC₆H₄NMe₂)₂CH]⁻