Characterization alkoxides

Kuhlman R., Vaarstra B.A., Streib W.E., Huffman J.C., Caulton K.G. Primary steps in the hydrolyses of two heterometallic alkoxides. Characterization of lithium-titanium and barium-zirconium isopropoxides [LiTiO(0-wo-Pr)3]4 and BaZr4(OH)(O-W0-Pr)i7. Inorg. Chem. 1993 32 ... 

P-Keto esters are characterized by pK s of about 11 and are quantitatively converted to their- enolates on treatment with alkoxide bases. 

Mercaptides and alkoxides have been shown to react with iminium salts, but the products have been shown to be unstable (48). Only one compound has been isolated and characterized and that is the adduct of p-thiocresol potassium salt. The adduct (82) decomposed on standing in air or on treatment with dilute acids to give back the -thiocresol (48). 

Alkoxides of all 3 metals are well characterized but it is those of titanium which are of particular importance. The solvolysis of TiCU with an alcohol yields a dialkoxide ... 

Very recently, Wilkes and co-workers 330,331) have reported the preparation and characterization of hybrid materials, which they named as ceramers . Ceramers were synthesized through the incorporation of polymeric or oligomeric PDMS into silicate glasses by a sol-gel process as shown in Reaction Scheme XXIV. During these reactions the variables such as the type of the alkoxide used, amount of water added, the pH value of the reaction system, and the reaction temperature, were carefully monitored. 

The catalysts that allow the production of maleic anhydride from n-butane with high selectivity, like (V0)2P207, are characterized by a strong acidity, that, like a strong basicity, favors the decomposition of alkoxides to give the olefin and the diene. The catalysts that allow the production of maleic anhydride, either from n-butane or from butenes and butadiene, necessarily have particular sites that allow the insertion of oxygen atoms in the 1,4-position of butadiene. These sites are definitely absent on combustion catalysts. 

The mechanism of [3 + 2] reductive cycloadditions clearly is more complex than other aldehyde/alkyne couplings since additional bonds are formed in the process. The catalytic reductive [3 + 2] cycloaddition process likely proceeds via the intermediacy of metallacycle 29, followed by enolate protonation to afford vinyl nickel species 30, alkenyl addition to the aldehyde to afford nickel alkoxide 31, and reduction of the Ni(II) alkoxide 31 back to the catalytically active Ni(0) species by Et3B (Scheme 23). In an intramolecular case, metallacycle 29 was isolated, fully characterized, and illustrated to undergo [3 + 2] reductive cycloaddition upon exposure to methanol [45]. Related pathways have recently been described involving cobalt-catalyzed reductive cyclo additions of enones and allenes [46], suggesting that this novel mechanism may be general for a variety of metals and substrate combinations. 

So far the results have been shown in which the metal alkoxide solutions are reacted in the open system. It has been shown that the metal alkoxide solutions reacted in the closed container never show the spinnability even when the starting solutions are characterized by the low acid content and low water content (4). It has been also shown from the measurements of viscosity behavior that the solution remains Newtonian in the open system, while the solution exhibits structural viscosity (shear-thinning) in the closed system. 

Cobalt(II) alkoxides are known and monomeric forms are part of a wider review.413 The interest in these compounds pertains to a potential role in catalysis. For example, a discrete cobalt(II) alkoxide is believed to form in situ from a chloro precursor during reaction and performs the catalytic role in the decomposition of dialkyl pyrocarbonates to dialkyl carbonates and carbon dioxide.414 A number of mononuclear alkoxide complexes of cobalt(II) have been characterized by crystal structures, as exemplified by [CoCl(OC(t-Bu)3)2 Li(THF)].415 The Co ion in this structure and close relatives has a rare distorted trigonal-planar coordination geometry due to the extreme steric crowding around the metal. 

Zinc hydroxide and alkoxide species are particularly relevant to catalytic processes, often forming the active species. The cooperative effects of more than one zinc ion and bridged hydroxides are exploited in some enzymatic systems. Zinc alkyl phosphate and carboxylate materials have been important in the formation of framework compounds, often containing large amounts of free space for the inclusion of guest molecules. Aldehyde and ketone compounds are of low stability due to the poor donor capabilities of the ligands however, a number of examples have recently been characterized. 

Zinc alkoxide and aryloxide complexes have been of particular interest as enzyme models and catalysts. Tetrameric alkyl zinc alkoxides are a common structurally characterized motif.81... 

A series of zinc alkoxide complexes were characterized of the form [RZnOR ]ra where n 2 or 4 (Figure 4). Complexes of the form [Zn3 0(2,6-i-Pr2C6H3) 4R2] were produced by stoichiometry... 

Kimura and co-workers have synthesized a series of alkoxide complexes with the alcohol functionality as a pendent arm.447 674 737 A zinc complex of l-(4-bromophenacyl)-l, 4,7,10-tetraaza-cyclododecane was also synthesized by the same workers to mimic the active site of class II aldolases. The X-ray structure shows a six-coordinate zinc center with five donors from the ligand and a water molecule bound. The ketone is bound with a Zn—O distance of 2.159(3) A (Figure 12). Potentiometric titration indicated formation of a mixture of the hydroxide and the enolate. Enolate formation was also independently carried out by reaction with sodium methoxide, allowing full characterization.738... 

The conclusions derived from the preceding experiments may be summarized with the aid of the reaction mechanism illustrated in Scheme II. The ester undergoes a rapid, reversible association with the cycloamylose, C—OH. An alkoxide ion derived from a secondary hydroxyl group of the cycloamylose may then react with an included ester molecule to liberate a phenolate ion and produce an acylated cycloamylose. This reaction is characterized by a rate constant, jfc2(lim), the maximal rate constant for the appearance of the phenolate ion from the fully complexed ester in the pH range where the cycloamylose is completely ionized. Limiting rates are seldom achieved, however, because of the high pK of cycloamylose. 

A series of bis(phenoxide) aluminum alkoxides have also been reported as lactone ROP initiators. Complexes (264)-(266) all initiate the well-controlled ROP of CL, NVL.806,807 and L-LA.808 Block copolymers have been prepared by sequential monomer addition, and resumption experiments (addition of a second aliquot of monomer to a living chain) support a living mechanism. The polymerizations are characterized by narrow polydispersities (1.20) and molecular weights close to calculated values. However, other researchers using closely related (267) have reported Mw/Mn values of 1.50 and proposed that an equilibrium between dimeric and monomeric initiator molecules was responsible for an efficiency of 0.36.809 In addition, the polymerization of LA using (268) only achieved a conversion of 15% after 5 days at 80 °C (Mn = 21,070, Mn calc 2,010, Mw/Mn = 1.46).810... 

Wi ( p-H)2 (O-i-Pr) m (30) is one of the very few transition metal hydrido alkoxides that have been claimed in the literature (58,59). It is the only one to be fully structurally characterized by an X-ray study and, though in the solid state each tungsten is in a distorted octahedral environment (Figure 4), it behaves in solution as a coordinatively unsaturated... 

Boyle, T. J. Pearson, A. T. Schwartz, R. W. 1994. Synthesis and characterization of Group IV metal adamantanol alkoxides as potential PZT precursors. Ceram. Trans. 43 79-87. 

A], Alkoxide/oxide compounds of the speculated general formula BiO(OOCR) are formed by dissolving Bi203 in the carboxylic acid, followed by dilution and distillation of the excess acid (59). The compounds were characterized by elemental analysis and preliminary X-ray diffraction data. 

A variety of derivatives of bis-[Bi(tr)2X, X = Cl or N03], tris-(Bitr3), and tetra-([Bi(tr)4X][Na]) tropolonate complexes of bismuth (178, 179) have been prepared and spectroscopically characterized (176, 177, 180). Solid-state structures for examples of bis-(tropolonate) derivatives confirm the chelate interaction (171) and in the case of the nitrate derivative, reveal intermolecular alkoxide-bismuth [Bi-0 2.688 and 2.666 A] dimer contacts 52, which are slightly longer than the chelate bonds [Bi-0 2.130-2.323 A],... 

The cationic tantalum dihydride Cp2(CO)Ta(H)2]+ reacts at room temperature with acetone to generate the alcohol complex [Cp2(C0)Ta(H01Pr)]+, which was isolated and characterized [45]. The mechanism appears to involve protonation of the ketone by the dihydride, followed by hydride transfer from the neutral hydride. The OH of the coordinated alcohol in the cationic tantalum alcohol complex can be deprotonated to produce the tantalum alkoxide complex [Cp2(C0)Ta(01Pr)]. Attempts to make the reaction catalytic by carrying out the reaction under H2 at 60 °C were unsuccessful. The strong bond between oxygen and an early transition metal such as Ta appears to preclude catalytic reactivity in this example. 

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