Imidazolium ions

Given that the p/Ca of imidazolium ion is 7 is a 1 M aqueous solution of imidazolium chloride acidic basic or neutraP What about a 1 M solu tion of imidazole A solution containing equal molar quantities of imidazole and imidazolium chloride ... 

Imidazolium halides pyrolysis, 5, 449 Imidazolium ions acylation, 5, 402 H NMR, 5, 352 hydrogen exchange, 5, 417 nucleophilic attack, 5, 375 reactivity, 5, 375 ring opening, S, 375 Imidazolium oxides in pyrrole synthesis, 4, 344 Imidazolium perchlorate, 1,3-diphenyl-acylation, 5, 402 Imidazolium salts 1-acetyl-... 

These are typical of ionic liquids and are familiar in simulations and theories of molten salts. The indications of structure in the first peak show that the local packing is complex. There are 5 to 6 nearest neighbors contributing to this peak. More details can be seen in Figure 4.3-3, which shows a contour surface of the three-dimensional probability distribution of chloride ions seen from above the plane of the molecular ion. The shaded regions are places at which there is a high probability of finding the chloride ions relative to any imidazolium ion. 

The first reaction pathway for the in situ formation of a metal-carbene complex in an imidazolium ionic liquid is based on the well loiown, relatively high acidity of the H atom in the 2-position of the imidazolium ion [29]. This can be removed (by basic ligands of the metal complex, for example) to form a metal-carbene complex (see Scheme 5.2-2, route a)). Xiao and co-workers demonstrated that a Pd imida-zolylidene complex was formed when Pd(OAc)2 was heated in the presence of [BMIMjBr [30]. The isolated Pd carbene complex was found to be active and stable in Heck coupling reactions (for more details see Section 5.2.4.4). Welton et al. were later able to characterize an isolated Pd-carbene complex obtained in this way by X-ray spectroscopy [31]. The reaction pathway to the complex is displayed in Scheme 5.2-3. 

In the author s group, much lower-melting benzenesulfonate, tosylate, or octyl-sulfate ionic liquids have recently been obtained in combination with imidazolium ions. These systems have been successfully applied as catalyst media for the biphasic, Rh-catalyzed hydroformylation of 1-octene [14]. The catalyst activities obtained with these systems were in all cases equal to or even higher than those found with the commonly used [BMIM][PF6]. Taking into account the much lower costs of the ionic medium, the better hydrolysis stability, and the wider disposal options relating to, for example, an octylsulfate ionic liquid in comparison to [BMIM][PF6], there is no real reason to center future hydroformylation research around hexafluorophosphate ionic liquids. 

On intuition, a minute amount of water was added to the solvent (ethyl acetate) in the first crystallization experiment containing a molar excess of imidazole corresponding to 1, Regularly shaped crystals were formed within one hour. Such a crystal, subjected to X-ray analysis, has the structure as shown in Fig. 41 U1). Apart from the formation of the expected salt-type associate (carboxylate-imidazolium ion pair, cf. Sect. 4.2.2), two water molecules are present in the asymmetric unit of the crystal structure. This fact called our attention again to the family of serine protease enzymes, where water molecules are reported as being located in the close vicinity of the active sites 115-120),... 

Instead, the conformational characteristics are explained by the stringent requirement of the ionic interaction between the carboxylate/imidazolium ion pair coupled with the attempt of the former group to maintain as many H-bonds as possible (e.g. four H-bonds, cf. Ref. 75c). Such an attempt is obviously supported by the intramolecular H-bond in 1 Im 2 H20. The geometry of the corresponding moieties indicates the presence of strongly interacting ionic species (Fig. 42). 

The mechanism of hydrolysis of cysteine peptidases, in particular cysteine endopeptidases (EC 3.4.22), shows similarities and differences with that of serine peptidases [2] [3a] [55 - 59]. Cysteine peptidases also form a covalent, ac-ylated intermediate, but here the attacking nucleophile is the SH group of a cysteine residue, or, rather, the deprotonated thiolate group. Like in serine hydrolases, the imidazole ring of a histidine residue activates the nucleophile, but there is a major difference, since here proton abstraction does not appear to be concerted with nucleophilic substitution but with formation of the stable thiolate-imidazolium ion pair. Presumably as a result of this specific activation of the nucleophile, a H-bond acceptor group like Glu or Asp as found in serine hydrolases is seldom present to complete a catalytic triad. For this reason, cysteine endopeptidases are considered to possess a catalytic dyad (i.e., Cys-S plus H-His+). The active site also contains an oxyanion hole where the terminal NH2 group of a glutamine residue plays a major role. 

Miller and co-workers have taken a totally different approach to design an efficient catalyst for enantioselective acylation. Their strategy relied on the use of a pep-tide-based backbone incorporating a 3-(l-imidazolyl)-(5)-alanine unit as the catalytic core. Upon treatment with an achiral acyl source these biomimetic enantioselective acyl transfer catalysts allow the formation of an acyl imidazolium ion in proximity to the chiral environment generated by the folding of the peptide [3, 159-174]. 

A number of other substituted imidazolium ions have also been reported. [MIM-C2H50CH3]Br and [MIM-CH30CH3]Br, liquids at room temperature, were recently reported to be good solvents for carbohydrates and proteins (47). The diversity of organic cations was extended even to include the antifungal drug miconazole, which contains an imidazole ring. By the reaction of the miconazole with alkyl iodide, bioactive cations were obtained that were subsequently used to form ionic liquids with PF (9). 

Cholin chloride, shown in Scheme 1, was recently shown to be a versatile cationic precursor for the preparation of a wide variety of ionic liquids (48). This precursor is particularly interesting, as cholin is a vitamin B4 additive to animal food. Therefore, it is not expected to be restricted in applications by health-related concerns, whereas a number of other ionic liquids remain to be fully evaluated for their environmental and health effects, including the ones based on imidazolium ions. 

It has been noted that imidazolium ions are not inert. Under mild basic conditions, they are deprotonated to give reaetive nucleophiles. For reactions in basic media, the C2 hydrogen of the imidazolium ring can be replaced with an alkyl group. In one study, the C2 hydrogen was substituted by a methyl group. Ionie liquids based on the C2 methylated imidazolium cation were evaluated for the... 

According to a different approach to tailoring a catalyst for the desired ionic character, the catalyst was modified by the attachment of an imidazolium ion. This approach was demonstrated for a vanadyl salen complex, VO(salen) IL (Scheme 14) (187). 

The first group 13 (IIIA) element-carbene complex to be reported was an imi-dazol-2-ylidene-alane complex (Scheme 8.23). Based on NMR data, it was suggested that the imidazole fragment has an electronic structure that is intermediate between those of the free carbene and imidazolium ion. The use of an imidazol-2-... 

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