Structure–Reactivity Relationship in Organolithium Compounds

Carl, Elena

doi:10.1002/9783527667512.ch1

Cited by 21 publications

(15 citation statements)

References 81 publications

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“…This is because of the weak nucleophilicity of bulky lithium amides combined with a high basicity, making them excellent metallation reagents, even for vaguely acidic C–H bonds. 1 Furthermore, lithium amides can serve as catalysts, e.g. in the hydro-amination reaction, as described by Hultzsch et al 2 Their reactivity is determined by their structure, which in turn is influenced by solvation, adjusting the aggregation.…”

Section: Introductionmentioning

confidence: 99%

Benchmarking lithium amideversusamine bonding by charge density and energy decomposition analysis arguments

et al. 2018

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Section: Introductionmentioning

confidence: 99%

Benchmarking lithium amideversusamine bonding by charge density and energy decomposition analysis arguments

et al. 2018

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“…Alkali-metal alkyls are key compounds in organic synthesis and have shown enormous utility in the preparation of a range of organometallic compounds through salt metathesis reactions. Formation of alkyl derivatives of heavier alkali metals as reactive intermediates is often assumed in superbase chemistry .…”

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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“…Currently, it is commonly considered as very polar. The structure formation principles have been reviewed various times, − and the structure reactivity relation was studied on numerous occasions. , Anyhow, apart from a few examples (i.e., [( R , S )-(ABCO)LiC(H)PhSiMe 2 CH 2 N(C 4 H 7 )CH 2 OMe], ABCO = quinuclidine, N(CH 2 CH 2 ) 3 CH, [(PicH)LiPic] 2 , Pic = picolyl, and [(THF)Li 2 {H 2 CS(N t Bu) 2 }] 2 ), the overwhelming majority of organolithium structures have only been analyzed with the help of the classical Independent Atom Model (IAM). Unfortunately, the most important properties of a molecule cannot be deduced from that model. , The experimental charge density determination as a particularly demanding and precise diffraction experiment yet opens the avenue to the comprehensive understanding of the structure/property relation. , In the discussion of routine structure determinations, the anticipated reactivity and materials’ properties are indirectly extrapolated from the comparison of the geometrical features (bond distances, conformation, hydrogen-bond networks, noncovalent interactions, etc.)…”

Section: Introductionmentioning

confidence: 99%

“…The structure formation principles have been reviewed various times, 28−31 and the structure reactivity relation was studied on numerous occasions. 32,33 Anyhow, apart from a few examples (i.e., [(R,S)-(ABCO)LiC(H)-PhSiMe 2 CH 2 N(C 4 H 7 )CH 2 OMe], 34 ABCO = quinuclidine, N(CH 2 CH 2 ) 3 CH, [(PicH)LiPic] 2 , 35 Pic = picolyl, and [(THF)Li 2 {H 2 CS(N t Bu) 2 }] 2 36 ), the overwhelming majority of organolithium structures have only been analyzed with the help of the classical Independent Atom Model (IAM). Unfortunately, the most important properties of a molecule cannot be deduced from that model.…”

Section: ■ Introductionmentioning

confidence: 99%

Insight into the Bonding and Aggregation of Alkyllithiums by Experimental Charge Density Studies and Energy Decomposition Analyses

et al. 2020

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In this Article, the organolithiums [((−)-sparteine)-Li t Bu] (1), [(ABCO)Li t Bu] 2 (2), and [(ABCO) 2 (Li i Pr) 4 ] (3) are investigated by means of experimental and theoretical charge density determination to elucidate the nature of the Li−C and Li− N bonds. Furthermore, the valence shell charge concentrations (VSCCs) in the nonbonding region of the deprotonated C α -atom will provide some insight on the localization of the carbanionic lone pair. Analysis of the electron density (ρ(r BCP )), Laplacian (∇ 2 ρ(r BCP )), and the energy decomposition (EDA) confirmed that the Li−C/N bond exhibits astonishingly similar characteristics, to reveal an increasingly polar contact with decreasing aggregate size. This explains former observations on the incorporation of halide salts in organolithium reagents. Furthermore, it could be shown that the bonding properties of the i Pr group are similar to those of the t Bu substituent. The accuracy of fit to all previously determined properties in organolithiums is remarkable.

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Structure–Reactivity Relationship in Organolithium Compounds

Cited by 21 publications

References 81 publications

Benchmarking lithium amideversusamine bonding by charge density and energy decomposition analysis arguments

Benchmarking lithium amideversusamine bonding by charge density and energy decomposition analysis arguments

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

Insight into the Bonding and Aggregation of Alkyllithiums by Experimental Charge Density Studies and Energy Decomposition Analyses

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Structure–Reactivity Relationship in Organolithium Compounds

Cited by 21 publications

References 81 publications

Benchmarking lithium amideversusamine bonding by charge density and energy decomposition analysis arguments

Benchmarking lithium amideversusamine bonding by charge density and energy decomposition analysis arguments

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

Insight into the Bonding and Aggregation of Alkyllithiums by Experimental Charge Density Studies and Energy Decomposition Analyses

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