Metal oxide salt elimination reactions

Many alkoxides in particular have been known since the 1960s, but interest in them has been stimulated recently by their potential use as precursors for deposition of metal oxides using the sol-gel or MOCVD process. A review covering the literature to 1990 has appeared. " Traditionally, alkoxides are made by salt-elimination reactions of lanthanide chlorides with alkali metal alkoxides (or aryloxides) which sometimes causes chloride retention... 

Scheme 7.8 General synthetic strategy for incorporating metal-metal bonds into polymer backbones using oxidation or reduction and salt elimination reactivity. See text for details about the oxidation and reduction reactions and about the salt elimination reactions.

In general, the diazabutadienideo compound [Ga N(R)C(H) 2] undergoes substitution or salt elimination reactions with metal derivatives, while the main synthetic routes to Ga(Giso) and Ga(DDP) complexes are substitution or oxidative addition reactions [48]. 

Lithium Iodide. Lithium iodide [10377-51 -2/, Lil, is the most difficult lithium halide to prepare and has few appHcations. Aqueous solutions of the salt can be prepared by carehil neutralization of hydroiodic acid with lithium carbonate or lithium hydroxide. Concentration of the aqueous solution leads successively to the trihydrate [7790-22-9] dihydrate [17023-25-5] and monohydrate [17023-24 ] which melt congmendy at 75, 79, and 130°C, respectively. The anhydrous salt can be obtained by carehil removal of water under vacuum, but because of the strong tendency to oxidize and eliminate iodine which occurs on heating the salt ia air, it is often prepared from reactions of lithium metal or lithium hydride with iodine ia organic solvents. The salt is extremely soluble ia water (62.6 wt % at 25°C) (59) and the solutions have extremely low vapor pressures (60). Lithium iodide is used as an electrolyte ia selected lithium battery appHcations, where it is formed in situ from reaction of lithium metal with iodine. It can also be a component of low melting molten salts and as a catalyst ia aldol condensations. 

Alcohols react with boric acid with elimination of water to form borate esters, B(OR)3. A wide variety of borate salts and complexes have been prepared by the reaction of boric acid and inorganic bases, amines, and heavy-metal cations or oxyanions (44,45). Fusion with metal oxides yields... 

Dehalogenation of monochlorotoluenes can be readily effected with hydrogen and noble metal catalysts (34). Conversion of -chlorotoluene to Ncyanotoluene is accompHshed by reaction with tetraethyl ammonium cyanide and zero-valent Group (VIII) metal complexes, such as those of nickel or palladium (35). The reaction proceeds by initial oxidative addition of the aryl haHde to the zerovalent metal complex, followed by attack of cyanide ion on the metal and reductive elimination of the aryl cyanide. Methylstyrene is prepared from -chlorotoluene by a vinylation reaction using ethylene as the reagent and a catalyst derived from zinc, a triarylphosphine, and a nickel salt (36). 

The water elimination reactions of Co3(P04)2 8 H20 [838], zirconium phosphate [839] and both acid and basic gallium phosphates [840] are too complicated to make kinetic studies of more than empirical value. The decomposition of the double salt, Na3NiP3O10 12 H20 has been shown [593] to obey a composite rate equation comprised of two processes, one purely chemical and the other involving diffusion control, for which E = 38 and 49 kJ mole-1, respectively. There has been a thermodynamic study of CeP04 vaporization [841]. Decomposition of metal phosphites [842] involves oxidation and anion reorganization. 

From the preceding discussion, it is easily understood that direct polyesterifications between dicarboxylic acids and aliphatic diols (Scheme 2.8, R3 = H) and polymerizations involving aliphatic or aromatic esters, acids, and alcohols (Scheme 2.8, R3 = alkyl group, and Scheme 2.9, R3 = H) are rather slow at room temperature. These reactions must be carried out in the melt at high temperature in the presence of catalysts, usually metal salts, metal oxides, or metal alkoxides. Vacuum is generally applied during the last steps of the reaction in order to eliminate the last traces of reaction by-product (water or low-molar-mass alcohol, diol, or carboxylic acid such as acetic acid) and to shift the reaction toward the... 

The major synthetic routes to transition metal silyls fall into four main classes (1) salt elimination, (2) the mercurial route, a modification of (1), (3) elimination of a covalent molecule (Hj, HHal, or RjNH), and (4) oxidative addition or elimination. Additionally, (5) there are syntheses from Si—M precursors. Reactions (1), (2), and (4), but not (3), have precedence in C—M chemistry. Insertion reactions of Si(II) species (silylenes) have not yet been used to form Si—M bonds, although work may be stimulated by recent reports of MejSi 147) and FjSi (185). A new development has been the use of a strained silicon heterocycle as starting material (Section II,E,4). 

A reaction mechanism with Fe304 as catalyst has been proposed [68], in agreement with previous work concerning decarboxylation of acids in the presence of a metal oxide [83]. After the transient formation of iron(II) and iron(III) carboxylates from the diacid and Fe304 (with elimination of water), the thermal decarboxylation of these salts should give the cyclic ketone and regeneration of the catalyst. 

Dehydrohalogenation is generally carried out in solution, with a base, and the mechanism is usually E2, though the El mechanism has been demonstrated in some cases. However, elimination of HX can be accomplished by pyrolysis of the halide, in which case the mechanism is Ei (p. 1006) or, in some instances, the free-radical mechanism (p. 1008). Pyrolysis is normally performed without a catalyst at about 400°C. The pyrolysis reaction is not generally useful synthetically, because of its reversibility. Less work has been done on pyrolysis with a catalyst245 (usually a metallic oxide or salt), but the mechanisms here are probably El or E2. 

The most important synthetic routes continue to be (1) the elimination of an alkali halide between the salt of a transition-metal anion and a silicon halide, and (2) oxidative addition and addition-elimination reactions. The present position regarding the scope and limitations of these and other routes is outlined in this section. 

Relatively few germylarsines are known. They are usually prepared from the respective sUylarsine by a salt elimination or dehalosilylation reaction (equations 53-55). Cleavage of the Ge-N bond with a secondary arsine also leads to the formation of germylarsines (equation 56). Oxidation of the germylarsines with oxygen leads to the respective metal arsinates, R3Ge-0-As(0)R2. 

A second major route to metal-metal complexes, related to the salt-elimination method described above, is elimination of neutral molecules with concurrent formation of metal-metal bonded complexes. Transihon metal hydrides readily undergo these dinuclear reductive elimination reactions. The oxidative addition/reductive elimination see Oxidative Addition and Reductive Elimination) reaction of molecular hydrogen is a key reachon in this area (equation 47). 

If a wet method for collection is selected, such as a wet electrostatic precipitator, fiber-type self-draining mist eliminator, or wet scrubber, ammonia can be regenerated from the salt solution by reaction with a readily available metal oxide such as lime or zinc oxide with formation of a stable sulfur product for disposal. These metal oxides, however, as well as their reaction products, are insoluble and could cause deposition on heat transfer surfaces and/or clogging in the regenerating equipment. Therefore, as indicated in Figure 2, to ensure continuity and reliability of the process, a soluble metal oxide was utilized (in the form of sodium hydroxide solution) to regenerate the ammonia in the experimental work described. This procedure also allows more eflFective utilization of the metal oxide the soluble oxide (NaOH) can be regenerated in batch equipment outside the continuous portion of the process by reaction with either the aforestated insoluble reactants, lime, or zinc oxide. Better control is aflForded in a batch reactor with more eflBcient use of reactants. However, in full-scale equipment undersirable deposition of reactant and product may be controllable so that batch operation may not be necessary. 

Reactions of transition metal carbonyls with an In(I) center also take place by oxidative addition here InX inserts into the M-X bond. Oxidative addition to the low-valent halides of Ga, In, or T1 thus provides a useful route to compounds with group IIIB-metal bonds This approach is particularly useful when the salt elimination route cannot be employed because a suitable transition metal nucleophile is lacking. 

When the substrate is a triflate, or when a halide is subjected to appropriate reaction conditions in the presence of a halide scavenger (such as silver or thallium salts), the reaction proceeds via the cationic manifold. After oxidative addition, dissociation of X yields cationic intermediate 67. Alkene coordination provides 68 and migratory insertion delivers 69. /S-Hydride elimination then yields the desired product 66. Of importance in the pathway 62- 7— 68— 69— 66 is that both phosphines maintain contact with the metal throughout the process. This is ostensibly the factor responsible for the high enantioselectivities observed for reactions that are thought to proceed along this pathway. This contrasts with the course of events in the neutral pathway, where phosphine dissociation is thought to be responsible for low enantioselectivities. 

Most metal-boryl complexes have been synthesized by salt elimination or oxidative addition. Examples of these reactions are shown below. Ottier less common routes to metal-boryl complexes include transmetaUation of a boryl group from one transition metal to another and reactions of boranes with metal-olefin complexes. Boryl complexes have also been generated as intermediates in catalytic processes by "transmetaUation" of a metal halide with a diboron reagent. ... 

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