Cation-induced structural alterations in the organo alkali metal derivatives of triphenylmethane: a combined x-ray and NMR study of the potassium-cesium salts

Hoffmann, Daniele; Bauer, Daniel J.; Schleyer, Paul v. R.

doi:10.1021/om00028a038

Cited by 127 publications

(60 citation statements)

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“…This η 6 -bonding mode of an arene to a metal is a common structural feature in heavy alkali metal organo- metallic complexes and these K⋯arene(centroid) distances are similar to those found in related benzene-or toluene-solvated potassium amide complexes (range, 2.862-3.108 Å). 23,45,[53][54][55][56][57][58][59][60][61][62][63][64][65][66][67] The K 2 N 2 units in both the non-centrosymmetric 1 and centrosymmetric 2 resemble those of (KHMDS) 2 reported by Tesh and Hanusa. 33 2and 2.800(2) Å for 2, respectively; see Table 1].…”

Section: X-ray Diffraction Studiesmentioning

confidence: 92%

Exploring the solid state and solution structural chemistry of the utility amide potassium hexamethyldisilazide (KHMDS)

et al. 2017

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The structural chemistry of eleven donor complexes of the important Brønsted base potassium 1,1,1,3,3,3-hexamethyldisilazide (KHMDS) has been studied. Depending on the donor, each complex adopted one of five general structural motifs. Specifically, in this study the donors employed were toluene (to give polymeric 1 and dimeric 2), THF (polymeric 3), N,N,N',N'-tetramethylethylenediamine (TMEDA) (dimeric 4), (R,R)-N,N,N',N'-tetramethyl-1,2-diaminocyclohexane [(R,R)-TMCDA] (dimeric 5), 12-crown-4 (dimeric 6), N,N,N',N'-tetramethyldiaminoethyl ether (TMDAE) (tetranuclear dimeric 8 and monomeric 10), N,N,N',N'',N''-pentamethyldiethylenetriamine (PMDETA) (tetranuclear dimeric 7), tris[2-dimethyl(amino)ethyl]amine (MeTREN) (tetranuclear dimeric 9) and tris{2-(2-methoxyethoxy)ethyl}amine (TMEEA) (monomeric 11). The complexes were also studied in solution by H andC NMR spectroscopy as well as DOSY NMR spectroscopy.

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Section: X-ray Diffraction Studiesmentioning

confidence: 92%

Exploring the solid state and solution structural chemistry of the utility amide potassium hexamethyldisilazide (KHMDS)

et al. 2017

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“…Compound 7 crystallizes in the orthorhombic space group Pbcn . The carbene carbon atom (C1) forms a double bond with para ‐carbon atom (C21) of the C 6 H 4 ring with respect to C27 11a. Thus, the C 6 H 4 ring adopts an unsymmetrically substituted functionalized 1,4‐quinodimethane with Me 2 cAAC at one side and CPh 2 at the para position.…”

Section: Methodsmentioning

confidence: 99%

Synthesis and Characterization of a Triphenyl‐Substituted Radical and an Unprecedented Formation of a Carbene‐Functionalized Quinodimethane

Mondal

Samuel

Roesky

et al. 2014

Chemistry A European J

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The trichlorosilylcarbene monoradical (Cy-cAAC ·)SiCl3 (1) was directly converted to (Cy-cAAC ·)SiPh3 (2) by substitution of the three chlorine atoms with phenyl groups without affecting the radical center adjacent to the silicon atom. In addition to the structure determination, compound 2 was studied by EPR spectroscopy and DFT calculations. The three hyperfine lines in the EPR spectrum of 2 are due to the coupling with (14)N nucleus. Functionalized 1,4-quinodimethane Me2-cAAC=C6H4=CPh2 (7) was isolated, whereas carbon analogue of radical 2 was targeted. Cyclic voltammogram of 7 indicated that a stable radical-anion 7 ·-, as well as a radical-cation 7 ·+, can be prepared. Theoretical calculations showed that one-electron ionization energy and electron affinity of 7 are 5.1 and 0.7 eV mol(-1), respectively.

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“…In connection with alkyl compounds of rubidium and cesium this route seems to be less appropriate because of less versatile and less easily accessible corresponding alkyl compounds. [15] Structurally characterised rubidium and cesium alkyl compounds include those with methyl, [16] tris(trimethylsilyl)methyl, [17] tris(dimethylphenyl)methyl, [18] bis(trimethylsilyl)methyl, [19,20] diphenylmethyl [21] and triphenylmethyl [22] groups. [15] Structurally characterised rubidium and cesium alkyl compounds include those with methyl, [16] tris(trimethylsilyl)methyl, [17] tris(dimethylphenyl)methyl, [18] bis(trimethylsilyl)methyl, [19,20] diphenylmethyl [21] and triphenylmethyl [22] groups.…”

Section: Introductionmentioning

confidence: 99%

Adding Rubidium and Cesium to the Homologous Series of Alkali Metal Compounds of (Trimethylsilyl)methanides and 2,2,6,6‐Tetramethylpiperidides

et al. 2012

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Keywords: Alkali metals / Metalation / Rubidium / Cesium / Carbanions / N-donor ligands (Trimethylsilyl)methylrubidium [RbCH 2 SiMe 3 ] (1) and (trimethylsilyl)methylcesium [CsCH 2 SiMe 3 ] (2) were prepared by metathesis reactions of (trimethylsilyl)methyllithium [LiCH 2 SiMe 3 ] with rubidium or cesium tert-butoxide in nhexane. Both new compounds are pyrophoric powders which were characterised by NMR spectroscopy and elemental analyses. They can be used as deprotonating agents towards secondary amines such as 2,2,6,6-tetramethylpiperidine (TMPH). The resulting amides [RbTMP] (3) and [CsTMP] (4) form temperature-sensitive, n-hexane-insoluble orange solids. Treatment with the bidentate donor N,N,NЈ,NЈ-tetra- [a]

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Cation-induced structural alterations in the organo alkali metal derivatives of triphenylmethane: a combined x-ray and NMR study of the potassium-cesium salts

Cited by 127 publications

References 0 publications

Exploring the solid state and solution structural chemistry of the utility amide potassium hexamethyldisilazide (KHMDS)

Exploring the solid state and solution structural chemistry of the utility amide potassium hexamethyldisilazide (KHMDS)

Synthesis and Characterization of a Triphenyl‐Substituted Radical and an Unprecedented Formation of a Carbene‐Functionalized Quinodimethane

Adding Rubidium and Cesium to the Homologous Series of Alkali Metal Compounds of (Trimethylsilyl)methanides and 2,2,6,6‐Tetramethylpiperidides

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