Search results for "Protonation"
showing 10 items of 583 documents
A theoretical study of carbon-carbon bond formation by a Michael-type addition.
2012
A theoretical study of the Michael-type addition of 1,3-dicarbonyl compounds to α,β-unsaturated carbonyl compounds has been performed in the gas phase by means of the AM1 semiempirical method and by density functional theory (DFT) calculations within the B3LYP and M06-2X hybrid functionals. A molecular model has been selected to mimic the role of a base, which is traditionally used as a catalyst in Michael reactions, an acetate moiety to modulate its basicity, and point charges to imitate the stabilization of the negative charge developed in the substrate during the reaction when taking place in enzymatic environments. Results of the study of six different reactions obtained at the three di…
ChemInform Abstract: Gas-Phase and Solution Basicities of Some Alkyl 2,6-Dialkylphenyl Ketones: A Comparative Analysis.
2000
Abstract The gas-phase basicity of a number of alkyl 2,6-dialkylphenyl ketones (2,6-R2C6H3COR′) has been found to be almost insensitive to structural variations, as a result of a compensation of steric and electronic effects associated with the bulkiness and to the polarizability, respectively, of R and/or R′. On the contrary, the basicity in concentrated sulfuric acid undergoes, along the same series of compounds, a variation of nearly 8 pK units, as a consequence of steric inhibition of solvation of the protonated carbonyl as the main effect played by R and/or R′. The results in the condensed phase agree very nicely with recent findings relevant to some 4-substituted 2,6-dimethylacetophen…
Planar-Chiral 1,1 '-Diboryl Metallocenes: Diastereoselective Synthesis from Boryl Cyclopentadienides and Spin Density Analysis of a Diborylcobaltocene
2017
International audience; The reaction of nonsubstituted alkali metal cyclopentadienides with haloboranes leads to similar to 90:10 mixtures of isomeric diene products that can be deprotonated to give simple boryl cyclopentadienides. We extended this transformation to the sterically hindered lithium tert-butylcyclopentadienide 1 using FBMe(s)2 (Mes = 2,4,6-trimethylphenyl) and ClBCy2 as electrophiles. The boryl group is selectively introduced in the remote position to minimize steric congestion. The new boryl dienes are obtained as mixtures of isomers, and subsequent deprotonation with MeLi or LiHMDS affords the lithium 1,3-disubstituted cyclopentadienides Sa,b in yields over 95%. Direct asse…
Stereocontrol in Diphenylprolinol Silyl Ether Catalyzed Michael Additions : Steric Shielding or Curtin-Hammett Scenario?
2017
The enantioselectivity of amine-catalyzed reactions of aldehydes with electrophiles is often explained by simple steric arguments emphasizing the role of the bulky group of the catalyst that prevents the approach of the electrophile from the more hindered side. This standard steric shielding model has recently been challenged by the discovery of stable downstream intermediates, which appear to be involved in the rate-determining step of the catalytic cycle. The alternative model, referred to as Curtin-Hammett scenario of stereocontrol, assumes that the enantioselectivity is related to the stability and reactivity of downstream intermediates. In our present computational study, we examine th…
Decisive influence of substitution positions in molecular self-assembly
2014
Molecular self-assembly provides a versatile tool for creating functional molecular structures at surfaces. A rational design of molecular structure formation requires not only an in-depth understanding of the subtle balance between intermolecular and molecule-surface interactions, but might also involve considering chemical changes of the molecules, such as deprotonation. Here, we present a systematic investigation of a comparatively simple class of molecules, namely dihydroxybenzoic acid, which, nevertheless, enables creating a rich variety of structures when deposited onto calcite (10.4) held at room temperature. Based on non-contact atomic force microscopy measurements in ultra-high vac…
INSERTION OF ISOCYANIDES INTO THE PALLADIUM CARBON BOND OF C-2-PALLADATED HETEROCYCLES - SYNTHESIS OF TRANS-[PDCL(C(RN)=NR) (PPH3)2] COMPLEXES (RN = …
1985
The titles complexes trans-[PdCl{C(RN)NR}(PPh3)2] (RN = 2-pyridyl (2-py), R = p-C6H4OMe, Me; RN = 2-pyrazyl (2-pyz), R = p-C6H4OMe) can be prepared by reaction of the N-protonated compounds, cis-[PdCl2(RNH)(PPh3] (RNH = 2-pyridylium (2-pyH) or 2-pyrazylium (2-pyzH) group), with PPh3, followed by addition of the isocyanide CNR and deprotonation with triethylamine, in a molar ratio Pd/PPh3/CNR/NEt3 of 1/1/1/1.1. The reaction sequence involves the successive formation of the cationic intermediates trans-[PdCl(RNH)(PPh3)2]+, trans-[Pd(RNH)(CNR)(PPh3)2]2+ and trans-[Pd(RN)(CNR)(PPh3)2]+, which were isolated and characterized as perchlorate salts for RN = 2-pyridyl. In the final step the coordin…
Preparation and protonation of 2-pyrimidyl- and 2-pyrazylpalladium(II) complexes
1985
Abstract The oxidative addition of 2-chloropyrimidine or 2-chloropyrazine to [Pd(PPh 3 ) 4 ] yields a mixture of trans -[PdCl(C 4 H 3 N 2 - C 2 )(PPh 3 ) 2 ] (I) and [PdCl(μ-C 4 H 3 N 2 - C 2 , N 1 )(PPh 3 (II) (C 4 H 3 N 2 = 2-pyrimidyl or 2-pyrazyl group). The mononuclear complexes I are quantitatively converted into the binuclear species II upon treatment with H 2 O 2 . The reaction of II with HCl gives the N -monoprotonated derivatives cis -[PdCl 2 (C 4 H 4 N 2 - C 2 )(PPh 3 )] (III), from which the cationic complexes trans -[PdCl(C 4 H 4 N 2 - C 2 )(L) (L = PPh 3 , IV; PMe 2 Ph, V; PEt 3 , VI) can be prepared by ligand substitution reactions. Reversible proton dissociation occurs in so…
Chalcogenide-capped triiron clusters [Fe3(CO)9(μ3-E)2], [Fe3(CO)7(μ3-CO)(μ3-E)(μ-dppm)] and [Fe3(CO)7(μ3-E)2(μ-dppm)] (E = S, Se) as proton-reduction…
2019
Chalcogenide-capped triiron clusters [Fe3(CO)7(μ3-CO)(μ3-E)(μ-dppm)] and [Fe3(CO)7(μ3-E)2(μ-dppm)] (E = S, Se) have been examined as proton-reduction catalysts. Protonation studies show that [Fe3(CO)9(μ3-E)2] are unaffected by strong acids. Mono-capped [Fe3(CO)7(μ3-CO)(μ3-E)(μ-dppm)] react with HBF4.Et2O but changes in IR spectra are attributed to BF3 binding to the face-capping carbonyl, while bicapped [Fe3(CO)7(μ3-E)2(μ-dppm)] are protonated but in a process that is not catalytically important. DFT calculations are presented to support these protonation studies. Cyclic voltammetry shows that [Fe3(CO)9(μ3-Se)2] exhibits two reduction waves, and upon addition of strong acids, proton-reducti…
Inhibitoren der Korrosion (9) Nachweis der Sekundärinhibitoren bei einigen Sulfoxiden, Triphenylarsinoxid und einigen Sulfoniumsalzen
1971
Die Schutzwerte von Dibenzylsulf-oxyd und strukturell verwandten Ver-bindungen sowie von Triphenylarsin-oxyd werden bestimmt. Sulfoxyde und Arsinoxyde werden (a) nach Protonierung in die kathodischen Bereiche gefuhrt und (b) nach Elektronenaufnahme in die ko-ordinationsfahigen Sekundarinhibitoren (Thioather und tert. Arsine) umgewan-delt. Die Sekundarinhibitoren ziehen entweder auf das Metall auf und unter-drucken dann die Auflosung des Eisens oder werden nicht am Metall fixiert (z. B. Diphenylsulfid) und entfalten dann keinen Schutz. Im Falle des Dibenzyl-sulfoxyds konnen ca. 90% des einge-setzten Dibenzylsulfoxyds als Dibenzyl-sulfid vom Eisen abgelost werden; 16% an unverandertem Dibenzy…
Photoredox-catalyzed synthesis of N-unsubstituted enaminosulfones from vinyl azides and sulfinates
2021
Abstract A metal-free visible light photoredox-catalyzed synthesis of N-unsubstituted enaminosulfones from vinyl azides and sodium sulfinates in moderate to high yields is described. The reaction proceeds in ethanol and uses eosin Y as a readily available photocatalyst in combination with nitrobenzene as an electron shuttle. Taking into account the number of steps involved (generation of the sulfonyl radical, its addition to the double bond, elimination of molecular nitrogen with formation of an iminyl radical, followed by its reduction and protonation) as well as the number of redox-active reaction partners involved, the selectivity of the process is quite impressive.