Complexes of alkoxides

Nakamoto K. Complexes of alkoxides, alcohols, ethers, ketones, aldehydes, esters and carboxylic groups, in Infrared and Raman spectra of inorganic and coordination compounds, Wiley, 2009, 62-67. 

General reviews of transition metal complexes of alkoxides, dialkylamides122 and nitrides123 showed that the main focus of attention was on the earlier transition metal elements, in particular, the Ti, V and Cr triads. 

The TT-allylpalladium complexes 241 formed from the ally carbonates 240 bearing an anion-stabilizing EWG are converted into the Pd complexes of TMM (trimethylenemethane) as reactive, dipolar intermediates 242 by intramolecular deprotonation with the alkoxide anion, and undergo [3 + 2] cycloaddition to give five-membered ring compounds 244 by Michael addition to an electron-deficient double bond and subsequent intramolecular allylation of the generated carbanion 243. This cycloaddition proceeds under neutral conditions, yielding the functionalized methylenecyclopentanes 244[148], The syn-... 

Enolate Initiators. In principle, ester enolate anions should represent the ideal initiators for anionic polymeri2ation of alkyl methacrylates. Although general procedures have been developed for the preparation of a variety of alkaU metal enolate salts, many of these compounds are unstable except at low temperatures (67,102,103). Usehil initiating systems for acrylate polymeri2ation have been prepared from complexes of ester enolates with alkak metal alkoxides (104,105). 

Double Alkoxides. Complex double alkoxides are formed when a solution of an alkaU or alkaline earth metal alkoxide is added to a solution of an alkoxide of aluminum, titanium, or tirconium and a series of such compounds have been prepared (44). 

More useful than the preceding methods is cleavage of alkoxides by acetyl chloride or bromide. One, two, three, or four alkoxyls can be replaced by chloride or bromide. Benzoyl chloride gives poor yields, however. The tri- and tetrachlorides, which are stronger Lewis acids than mono- and dichlorides, coordinate with the alkyl acetate formed and yield distillable complexes (46,55,56). 

Reactions of types (i)-(vi) can be catalyzed by alkoxide or hydroxide ions, or amines. Alternatively, an acid catalyst forms a complex of type (380) from which proton loss is facilitated. 

The neutral and anionic adducts of the halides constitute a large proportion of the complexes of Ti, and the alkoxides (also prepared from TiCU) are of commercial importance (p. 968). 

The next step in the calculations involves consideration of the allylic alcohol-carbe-noid complexes (Fig. 3.28). The simple alkoxide is represented by RT3. Coordination of this zinc alkoxide with any number of other molecules can be envisioned. The complexation of ZnCl2 to the oxygen of the alkoxide yields RT4. Due to the Lewis acidic nature of the zinc atom, dimerization of the zinc alkoxide cannot be ruled out. Hence, a simplified dimeric structure is represented in RTS. The remaining structures, RT6 and RT7 (Fig. 3.29), represent alternative zinc chloride complexes of RT3 differing from RT4. Analysis of the energetics of the cyclopropanation from each of these encounter complexes should yield information regarding the structure of the methylene transfer transition state. 

A Grignard reaction begins with an acid-base complexation of Vfg2+ to the carbonyl oxygen atom of the aldehyde or ketone, thereby making the carbonyl group a better electrophile. Nucleophilic addition of R then produces a tetrahedral magnesium alkoxide intermediate, and protonation by addition of water... 

The products in such cases contain complexes between M-butyl-magnesium chloride and the particular alkoxide employed. With the stated Low proportions of alkoxides, these complexes broadly resemble the alkoxide-free materials, but increased proportions of the alkoxide component give complexes having generally decreased chemical reactivity (see references 3 and 4). 

In the presence of alkoxides or amides, e.g., liberated during the preparation, ate complexes are reversibly formed and may modify the reactivity of the a-titanated 2-alkenyl carbamates17. 

Mn(II) > Mg(II).270 It should be underlined that titanium and zirconium alkoxides are efficient catalysts for both stages of reaction. Lanthanide compounds such as 2,2/-bipyridyl, acetylacetonate, and o-formyl phenolate complexes of Eu(III), La(III), Sm(III), Er(III), and Tb(III) appear to be even more efficient than titanium alkoxides, Ca or Mn acetates, Sb203, and their mixtures.273 Moreover, PET produced with lanthanides has been reported to exhibit better thermal and hydrolytic stability as compared to PET synthesized with the conventional Ca acetate -Sb203 catalytic system.273... 

Alcohols can be selectively bound to the same host type if they are combined with an amine and vice versa, considering that a cation and an anion will be formed through a proton transfer. The so-formed alkoxide anion will bind to the boron atom, while the ammonium ion will be complexed by the crown ether (147, Fig. 39). Competition experiments involving benzyl-amine have shown enhanced selectivity for the complexation of alcohols with... 

Either particulate sol or polymeric sol has been used for thin film coatings. The polymeric sol was fabricated by partial hydrolysis of corresponding metal alkoxide. If the rate of hydrolysis or condensation is very fast, then some kinds of organic acids, beta-dicarbonyls, and alkanolamines have been used as chelating agent in sol-gel processes to control the extent and direction of the hydrolysis-condensation reaction by forming a strong complex with alkoxide. [2]. 

Molecular precursors appropriate for use in the TMP method are typically oxygen-rich complexes of the form L M[OxE(OR) ]z, where L = alkoxide. 

Transfer hydrogenation of aldehydes with isopropanol without addition of external base has been achieved using the electronically and coordinatively unsaturated Os complex 43 as catalyst. High turnover frequencies have been observed with aldehyde substrates, however the catalyst was very poor for the hydrogenation of ketones. The stoichiometric conversion of 43 to the spectroscopically identifiable in solution ketone complex 45, via the non-isolable complex 44 (Scheme 2.4), provides evidence for two steps of the operating mechanism (alkoxide exchange, p-hydride elimination to form ketone hydride complex) of the transfer hydrogenation reaction [43]. 

It would be ideal if the asymmetric addition could be done without a protecting group for ketone 36 and if the required amount of acetylene 37 would be closer to 1 equiv. Uthium acetylide is too basic for using the non-protected ketone 36, we need to reduce the nucleophile s basicity to accommodate the acidity of aniline protons in 36. At the same time, we started to understand the mechanism of lithium acetylide addition. As we will discuss in detail later, formation of the cubic dimer of the 1 1 complex of lithium cyclopropylacetylide and lithium alkoxide of the chiral modifier3 was the reason for the high enantiomeric excess. However, due to the nature of the stable and rigid dimeric complex, 2 equiv of lithium acetylide and 2 equiv of the lithium salt of chiral modifier were required for the high enantiomeric excess. Therefore, our requirements for a suitable metal were to provide (i) suitable nucleophilicity (ii) weaker basicity, which would be... 

Many of the papers from Merck reported the 1 1 complex of lithium acetylide and lithium alkoxide of the chiral modifier as monomer and the dimer of the 1 1 complex as tetramer. 

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. 

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