MULTINUCLEAR MAGNETIC RESONANCE STUDY OF GROUP 14-SUBSTITUTED SULFUR DIIMIDES, AND THE MOLECULAR STRUCTURES OF DI-<i>tert</i>-BUTYL-, BIS(TRIPHENYLSILYL)- AND N-TRIMETHYLSILYL-N′-TRIPHENYLSILYL SULFUR DIIMIDE

Herberhold, Max; Gerstmann, Silke; Milius, Wolfgang; Wrackmeyer, Bernd; Borrmann, Horst

doi:10.1080/10426509608046369

Cited by 19 publications

(14 citation statements)

References 38 publications

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“…However, these SN bond lengths are in the range of other alkyl diimidosulfinates (1.598–1.657 Å) 15. In contrast to that, the SN distances in the corrdinated S(N t Bu) 2 ligand are considerably shorter (1.5331(15) and 1.5396(14) Å), so they are in the range of free, uncoordinated starting material 16. The distance between S3 and N8 is slightly longer (1.5396 Å) because of the coordination to the lithium atom.…”

Section: Resultsmentioning

confidence: 86%

Pd/Light‐Accelerated Atom‐Transfer Carbonylation of Alkyl Iodides: Applications in Multicomponent Coupling Processes Leading to Functionalized Carboxylic Acid Derivatives

Fusano

Sumino

Nishitani

et al. 2012

Chemistry A European J

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The atom-transfer carbonylation reaction of various alkyl iodides thereby leading to carboxylic acid esters was effectively accelerated by the addition of transition-metal catalysts under photoirradiation conditions. By using a combined Pd/hν reaction system, vicinal C-functionalization of alkenes was attained in which α-substituted iodoalkanes, alkenes, carbon monoxide, and alcohols were coupled to give functionalized esters. When alkenyl alcohols were used as acceptor alkenes, three-component coupling reactions, which were accompanied by intramolecular esterification, proceeded to give lactones. Pd-dimer complex [Pd(2)(CNMe)(6)][PF(6)](2), which is known to undergo homolysis under photoirradiation conditions, worked quite well as a catalyst in these three- or four-component coupling reactions. In this metal/radical hybrid system, both Pd radicals and acyl radicals are key players and a stereochemical study confirmed the carbonylation step proceeded through a radical carbonylation mechanism.

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Section: Resultsmentioning

confidence: 86%

Pd/Light‐Accelerated Atom‐Transfer Carbonylation of Alkyl Iodides: Applications in Multicomponent Coupling Processes Leading to Functionalized Carboxylic Acid Derivatives

Fusano

Sumino

Nishitani

et al. 2012

Chemistry A European J

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“…On the other hand all the SÀN bond lengths are found to be larger than the formal S=N bond length of 1.54 . [59,60] An X-ray crystal structure is available for Th-BBT. [31] The geometries determined by theory is compared with experimental ones for this molecule in Figure 1.…”

Section: Molecular Geometrymentioning

confidence: 99%

Substituents Destabilize the Molecule by Increasing Biradicaloid Character and Stabilize by Intramolecular Charge Transfer in the Derivatives of Benzobis(thiadiazole) and Thiadiazolothienopyrazine: A Computational Study

et al. 2011

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Keeping in view the possible applications of singlet open-shell molecules as semiconductors, non-classical derivatives of the heterocyclic rings benzobis(thiadiazole) (BBT) and its positional isomer thiadiazolothienopyrazine (TTP) are characterized using DFT methodologies. M06-2X, B3LYP and BHandHLYP functionals were used to optimize the geometries and estimate the vertical transition energies. It is observed that unlike the BHandHLYP functional (50% exchange), which gives rise to spin-contaminated solutions for all molecules in the series, M06-2X (54% exchange) affords a wavefunction either with no instability or negligible instability for most of the molecules. The results are compared with the earlier reported experimental data and those obtained herein using the spin-flip (SF)-5050 method. It is found that B3LYP does not fare well while on the other hand the M06-2X and SF-50-50 are in good agreement with the experimental results. It is seen that M06-2X TD-DFT for the molecules can be carried out without major spin contamination and also that the more time-consuming CI can be avoided for the calculation of transition energies. The biradical nature of the molecules is estimated by the singlet-triplet gap. Intramolecular charge transfer is calculated. It is found that the ring substituents donate charge in the ground state, creating a zwitterionic structure. Thus the substituents play an interesting dual role, decreasing the stability of the molecule by increasing the biradical character (small HOMO-LUMO gap), and stabilization of this ground state by intramolecular charge transfer.

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“…The nitrogen atoms of the pendant t BuN group show significantly shorter S−N distances [ 1 : 153.6(3) pm; 2 : 154.3(2) pm; 3 : 154.72(14) pm]. They are similar to the S=N double bonds in S(N t Bu) 2 (153.2 pm),21 but notably longer than in S(N t Bu) 3 (151.5 pm) 14. In general, the S−N bond lengths in 1 , 2 and 3 match the standard range for S VI −N bond lengths found in the CCDC (Scheme ) 22.…”

Section: Resultsmentioning

confidence: 95%

Heteroaromatic‐Substituted Mono‐ and Bis(triimidosulfonates)

Selinka

2003

Eur J Inorg Chem

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In this paper we present the syntheses and structures of the metal complexes [(THF)2Li{(NtBu)3S(C4H3NMe)}] (1), [(tmeda)Li{(NtBu)3S(C4H3S)}] (2), [(tmeda)Li{(NtBu)3S(C4H3Se)}] (3), [(THF)4Li2{(tBuN)3S(SC4H2)S(NtBu)3}] (4a) and [(tmeda)2Li2{(tBuN)3S(SC4H2)S(NtBu)3}] (4b). The lithium salts form non‐aggregated soluble molecules rather than infinite insoluble solid‐state lattices like their oxo analogues. The metals are N,N‐chelated rather than tripodally coordinated. Although the S−N bond to the one pendant spectator tBuN group is considerably shorter than in the metal‐coordinated tBuN groups, conjugation of the S−N bonds to the heteroaromatic rings could not be deduced unambiguously from the experimental structures. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

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MULTINUCLEAR MAGNETIC RESONANCE STUDY OF GROUP 14-SUBSTITUTED SULFUR DIIMIDES, AND THE MOLECULAR STRUCTURES OF DI-tert-BUTYL-, BIS(TRIPHENYLSILYL)- AND N-TRIMETHYLSILYL-N′-TRIPHENYLSILYL SULFUR DIIMIDE

Cited by 19 publications

References 38 publications

Pd/Light‐Accelerated Atom‐Transfer Carbonylation of Alkyl Iodides: Applications in Multicomponent Coupling Processes Leading to Functionalized Carboxylic Acid Derivatives

Pd/Light‐Accelerated Atom‐Transfer Carbonylation of Alkyl Iodides: Applications in Multicomponent Coupling Processes Leading to Functionalized Carboxylic Acid Derivatives

Substituents Destabilize the Molecule by Increasing Biradicaloid Character and Stabilize by Intramolecular Charge Transfer in the Derivatives of Benzobis(thiadiazole) and Thiadiazolothienopyrazine: A Computational Study

Heteroaromatic‐Substituted Mono‐ and Bis(triimidosulfonates)

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