By Don Bradley, R. C. Mehrotra, Ian Rothwell, A. Singh
This article relies on steel Alkoxides (Academic Press, 1978), and has been up-to-date and improved to incorporate advancements during this transforming into box from the previous two decades. assurance contains homometallic alkoxides; heterometallic alkoxides; x-ray crystal constructions of alkoxo steel compounds; steel oxo-alkoxides; steel aryloxides; and their commercial functions in such parts as microelectronics, ceramics, non-linear optical fabrics, high-temperature superconductors, and really good glasses. meant as a reference for these operating within the box, in addition to to be used as a supplementary textual content for complex inorganic chemistry classes.
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Additional info for Alkoxo and Aryloxo Derivatives of Metals
81 Preparation of organometal alkoxides of germanium,253 – 255 tin,256 – 266 and lead267,268 have also been described by the reactions of an appropriate organometal oxide or hydroxide with alcohols. 7 Alcohol Interchange (or Alcoholysis) Reactions of Metal(loid) Alkoxides (Method G) One of the characteristic features of metal(loid) alkoxides is their ability to exchange alkoxo groups with alcohols, and this has been widely exploited for the synthesis of new homo- and heteroleptic alkoxide derivatives of various s- , d- , f- , and p-block elements such as beryllium,219 yttrium,103,148 titanium,270 – 272 zirconium,135,273 – 276 hafnium,277 vanadium,249,278 niobium,279 – 281 tantalum,280 iron,282,283 copper,7,284,285 zinc,222 cerium,286,287 praseodymium,151 – 153 neodymium,151 – 153 samarium,155 gadolinium,103,156,157 erbium,103,156,157 ytterbium,103,148 thorium,141,287,288 uranium,289 – 291 boron,111,237,292 aluminium,293,294 gallium,184,185 indium,186 germanium,113,125,295 tin,296 – 300 antimony,301 and tellurium208,302 according to the general reaction (Eq.
Derivatives of the empirical formula M OR 3 are of special interest as, in these, association occurs primarily through the formation of metal–metal triple (MÁM) bonds359 rather than through the normal alkoxo bridges (Eq. 113) M2 NMe2 6 C >6ROH ! RO 3 MÁM(OR)3 C 6Me2 NH " (M D Mo, R D But ,360 Pri , CH2 But , CMe2 Ph, SiMe3 , SiEt3 ,361,362 menthyl;363 M D W; R D But 364,365 ). g. Mo2 (OR)6 (HNMe2 )2 , from which dimethylamine-free product could be obtained above 60Ž C under reduced pressure. However, the addition of excess EtOH to Mo2 NMe2 6 affords Mo4 (OEt)12 .
The reaction represented by Eq. 101) is, however, sometimes accompanied by a change in the oxidation state of the metal. For example, Cr(NEt2 )4 reacts with primary and secondary alcohols335 according to Eq. 107). Only tertiary alcohols and the sterically demanding 3,3-dimethyl-2-butanol,336 which are not prone to this type of oxidation, are known331 to give chromium(IV) alkoxides. 2Cr(NEt2 4 C 7R0 R00 CHOH ! 107 Similar to the alcoholysis reaction of tetrameric aluminium isopropoxide293 with tertbutyl alcohol, the alcoholysis reaction of dimeric aluminium tris(dimethyl amide)337,338 with tert-butyl alcohol is also slow owing to steric factors.