Hydrolysis, transition metals

Inspired by the many hydrolytically-active metallo enzymes encountered in nature, extensive studies have been performed on so-called metallo micelles. These investigations usually focus on mixed micelles of a common surfactant together with a special chelating surfactant that exhibits a high affinity for transition-metal ions. These aggregates can have remarkable catalytic effects on the hydrolysis of activated carboxylic acid esters, phosphate esters and amides. In these reactions the exact role of the metal ion is not clear and may vary from one system to another. However, there are strong indications that the major function of the metal ion is the coordination of hydroxide anion in the Stem region of the micelle where it is in the proximity of the micelle-bound substrate. The first report of catalysis of a hydrolysis reaction by me tall omi cell es stems from 1978. In the years that... 

The physical and chemical properties are less well known for transition metals than for the alkaU metal fluoroborates (Table 4). Most transition-metal fluoroborates are strongly hydrated coordination compounds and are difficult to dry without decomposition. Decomposition frequently occurs during the concentration of solutions for crysta11i2ation. The stabiUty of the metal fluorides accentuates this problem. Loss of HF because of hydrolysis makes the reaction proceed even more rapidly. Even with low temperature vacuum drying to partially solve the decomposition, the dry salt readily absorbs water. The crystalline soflds are generally soluble in water, alcohols, and ketones but only poorly soluble in hydrocarbons and halocarbons. 

The kinetics of hydrolysis reactions maybe first-order or second-order, depending on the reaction mechanism. However, second-order reactions may appear to be first-order, ie, pseudo-first-order, if one of the reactants is not consumed in the reaction, eg, OH , or if the concentration of active catalyst, eg, reduced transition metal, is a small fraction of the total catalyst concentration. 

The allyl group was used to protect the nitrogen in a /3-lactam synthesis, but was removed in a four-step sequence. Whether a transition-metal-catalyzed isomerization to the enamide followed by hydrolysis is an effective cleavage procedure remains to be tested and warrants further study. ... 

These transition metal carbenes, prepared in 66-97% yield from amino acid esters, are cleaved by acid hydrolysis (CF3CO2H, 20°, 80% yield 80% AcOH M = W BBr3,-25°). ... 

Lower oxidation states are rather sparsely represented for Zr and Hf. Even for Ti they are readily oxidized to +4 but they are undoubtedly well defined and, whatever arguments may be advanced against applying the description to Sc, there is no doubt that Ti is a transition metal . In aqueous solution Ti can be prepared by reduction of Ti, either with Zn and dilute acid or electrolytically, and it exists in dilute acids as the violet, octahedral [Ti(H20)6] + ion (p. 970). Although this is subject to a certain amount of hydrolysis, normal salts such as halides and sulfates can be separated. Zr and are known mainly as the trihalides or their derivatives and have no aqueous chemistry since they reduce water. Table 21.2 (p. 960) gives the oxidation states and stereochemistries found in the complexes of Ti, Zr and Hf along with illustrative examples. (See also pp. 1281-2.)... 

However, a number of limitations are still evident when tetrafluorohorate and hexafluorophosphate ionic liquids are used in homogeneous catalysis. The major aspect is that these anions are still relatively sensitive to hydrolysis. The tendency to anion hydrolysis is of course much less pronounced than that of the chloroalu-minate melts, hut it still occurs and this has major consequences for their use in transition metal catalysis. For example, the [PF ] anion of l-hutyl-3-methylimida-2olium ([BMIM]) hexafluorophosphate was found (in the author s laboratories) to hydrolyze completely after addition of excess water when the sample was kept for 8 h at 100 °C. Gaseous HF and phosphoric acid were formed. Under the same conditions, only small amounts of the tetrafluorohorate ion of [BMlMjjBFJ was converted into HF and boric acid [10]. The hydrolytic formation of HF from the anion of the ionic liquid under the reaction conditions causes the following problems with... 

The author anticipates that the further development of transition metal catalysis in ionic liquids will, to a significant extent, be driven by the availability of new ionic liquids with different anion systems. In particular, cheap, halogen-free systems combining weak coordination to electrophilic metal centers and low viscosity with high stability to hydrolysis are highly desirable. 

Recently, Deligoz and Yilmaz [51] prepared three polymeric calix[4]arenes, which were synthesized by reacting chloromethylated polystyrene with 25,26,27-tribenzoyloxy-28-hydroxy calix[4]arene (2a, 3a) and po-lyacryloyl chloride with 25,26,27,28-tetraacetoxy ca-lix[4]arene (4a). After alkaline hydrolysis of the polymers, they were utilized for selective extraction of transition metal cations from aqueous phase to organic phase. 

Base hydrolysis in transition-metal complexes. M. L. Tobe, Adv. Inorg. Bioinorg. Mech., 1983, 2,1 (269). 

Chiral epoxides and their corresponding vicinal diols are very important intermediates in asymmetric synthesis [163]. Chiral nonracemic epoxides can be obtained through asymmetric epoxidation using either chemical catalysts [164] or enzymes [165-167]. Biocatalytic epoxidations require sophisticated techniques and have thus far found limited application. An alternative approach is the asymmetric hydrolysis of racemic or meso-epoxides using transition-metal catalysts [168] or biocatalysts [169-174]. Epoxide hydrolases (EHs) (EC 3.3.2.3) catalyze the conversion of epoxides to their corresponding vicinal diols. EHs are cofactor-independent enzymes that are almost ubiquitous in nature. They are usually employed as whole cells or crude... 

Molecular nitrogen (N2) reacts with aryllithium compounds in the presence of compounds of such transition metals as titanium, chromium, molybdenum, or vanadium (e.g., TiCl4) to give (after hydrolysis) primary aromatic amines. ... 

In addition to activation of sihcon bonds by fluoride ions as discussed in Section 2.4, silicon-silicon, silicon-carbon, silicon-hydrogen, and silicon-nitrogen bonds are activated by transition metal salts and transition metal complexes. Thus, hydrolysis of silicon-carbon bonds such as in phenyltrimethylsilane 81 can be induced by... 

Employing ketones or aldehydes as starting materials, the corresponding silylethers are obtained. Thereafter, the oxidation or hydrolysis of the obtained silylethers gives the corresponding alcohols (Scheme 17). In most cases, a hydride (silyl) metal complex H-M-Si (M = transition-metal), which is generated by an oxidative addition of H-Si bond to the low-valent metal center, is a key intermediate in the hydrosilylation reaction. 

Gels of yttrium hydroxide are powerful catalysts for the hydrolysis of (76), and it was suggested that the hydroxide acts as a bifunctional general acid and nucleophile. The fact that gels of transition-metal hydroxides do not show comparable activity was attributed to their fixed co-ordination number, resulting in more rigid stereochemistry. 

The second general method, IMPR, for the preparation of polymer supported metal catalysts is much less popular. In spite of this, microencapsulation of palladium in a polyurea matrix, generated by interfacial polymerization of isocyanate oligomers in the presence of palladium acetate [128], proved to be very effective in the production of the EnCat catalysts (Scheme 3). In this case, the formation of the polymer matrix implies only hydrolysis-condensation processes, and is therefore much more compatible with the presence of a transition metal compound. That is why palladium(II) survives the microencapsulation reaction... 

Transition metal complexes containing Si-OH groups have been isolated in low yield after hydrolysis of the products formed in the reaction between (Me2N)2SiCl2 and ferrocene under Friedel-Crafts conditions [Eq. (25)] (151). 

In addition to the reactions discussed above, there are still other alkyne reactions carried out in aqueous media. Examples include the Pseudomonas cepacia lipase-catalyzed hydrolysis of propargylic acetate in an acetone-water solvent system,137 the ruthenium-catalyzed cycloisomerization-oxidation of propargyl alcohols in DMF-water,138 an intramolecular allylindination of terminal alkyne in THF-water,139 and alkyne polymerization catalyzed by late-transition metals.140... 

For the mechanism of azolide hydrolysis under specific conditions like, for example, in micelles,[24] in the presence of cycloamyloses,[25] or transition metals,[26] see the references noted and the literature cited therein. Thorough investigation of the hydrolysis of azolides is certainly important for studying the reactivity of those compounds in chemical and biochemical systems.[27] On the other hand, from the point of view of synthetic chemistry, interest is centred instead on die potential for chemical transformations e.g., alcoholysis to esters, aminolysis to amides or peptides, acylation of carboxylic acids to anhydrides and of peroxides to peroxycarboxylic acids, as well as certain C-acylations and a variety of other preparative applications. 

One of the chief defects of the phosphorus based pyrazolyl (PZ) ligands appears to be the hydrolytic sensitivity of the P—N bond particularly after interaction of the ligand with transition metal ions. The interactions of PhP(0)(3,5-Me2pz)2 and Ph2P(0)(3,5-Me2pz)2 with Pd11 salts accelerates the P—N bond hydrolysis.177... 

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