Group 11 Metal Carbonyls

Perhaps the most extensively studied catalytic reaction in acpreous solutions is the metal-ion catalysed hydrolysis of carboxylate esters, phosphate esters , phosphate diesters, amides and nittiles". Inspired by hydrolytic metalloenzymes, a multitude of different metal-ion complexes have been prepared and analysed with respect to their hydrolytic activity. Unfortunately, the exact mechanism by which these complexes operate is not completely clarified. The most important role of the catalyst is coordination of a hydroxide ion that is acting as a nucleophile. The extent of activation of tire substrate througji coordination to the Lewis-acidic metal centre is still unclear and probably varies from one substrate to another. For monodentate substrates this interaction is not very efficient. Only a few quantitative studies have been published. Chan et al. reported an equilibrium constant for coordination of the amide carbonyl group of... 

Reaction of TYZOR TPT with polyperfluoroalkylene ethers containing a carbonyl group produces a complex that is an excellent surface-treating agent, imparting improved surface wettabiUty and anticorrosion properties to metal surfaces (144). These complexes can be used by themselves, or as additives to perfluoropolyethers as vacuum pump oils, lubricant oils, or mold release agents. 

Formation of Functional Groups. Metal carbonyls have been used in a number of cases to synthesize organic molecules containing particular functional groups (147—149). A synthesis of olefins from -dihahdes has been reported (148) ... 

There are two distinct groups of aldolases. Type I aldolases, found in higher plants and animals, require no metal cofactor and catalyze aldol addition via Schiff base formation between the lysiae S-amino group of the enzyme and a carbonyl group of the substrate. Class II aldolases are found primarily ia microorganisms and utilize a divalent ziac to activate the electrophilic component of the reaction. The most studied aldolases are fmctose-1,6-diphosphate (FDP) enzymes from rabbit muscle, rabbit muscle adolase (RAMA), and a Zn " -containing aldolase from E. coli. In vivo these enzymes catalyze the reversible reaction of D-glyceraldehyde-3-phosphate [591-57-1] (G-3-P) and dihydroxyacetone phosphate [57-04-5] (DHAP). 

Many other organometaUic compounds also react with carbonyl groups. Lithium alkyls and aryls add to the ester carbonyl group to give either an alcohol or an olefin. Lithium dimethyl cuprate has been used to prepare ketones from esters (41). Tebbe s reagent, Cp2TiCH2AlCl(CH2)2, where Cp = clyclopentadienyl, and other metal carbene complexes can convert the C=0 of esters to C=CR2 (42,43). 

Transition metals have also been inserted into the aziridine ring affording derivatives (295). Stereochemical studies suggest that transfer of a proton is followed by bimolecular attack on the ring with subsequent closure on the carbonyl group (76AG(E)495). 

The final variable to be mentioned here is the presence of impurities. These may be metallic fragments residual from Ziegler-type processes or they can be trace materials incorporated into the polymer chain. Such impurities as catalyst fragments and carbonyl groups incorporated into the chain can have a serious adverse influence on the power factor of the polymer, whilst in other instances impurities can have an effect on aging behaviour. 

Friedrich et al. also used XPS to investigate the mechanisms responsible for adhesion between evaporated metal films and polymer substrates [28]. They suggested that the products formed at the metal/polymer interface were determined by redox reactions occurring between the metal and polymer. In particular, it was shown that carbonyl groups in polymers could react with chromium. Thus, a layer of chromium that was 0.4 nm in thickness decreased the carbonyl content on the surface of polyethylene terephthalate (PET) or polymethylmethacrylate (PMMA) by about 8% but decreased the carbonyl content on the surface of polycarbonate (PC) by 77%. The C(ls) and 0(ls) spectra of PC before and after evaporation of chromium onto the surface are shown in Fig. 22. Before evaporation of chromium, the C(ls) spectra consisted of two components near 284.6 eV that were assigned to carbon atoms in the benzene rings and in the methyl groups. Two additional... 

The alkoxide formed by attack of the carbonyl group of perfluorobutyrolactone opens the oxirane ring of hexafluoropropene oxide at the central carbon atom [37] (equation 33). A fluorinated sultone reacts with halogenoalkanes in the presence of metal fluoride [3S] (equation 34). 

Two classes of aldolase enzymes are found in nature. Animal tissues produce a Class I aldolase, characterized by the formation of a covalent Schiff base intermediate between an active-site lysine and the carbonyl group of the substrate. Class I aldolases do not require a divalent metal ion (and thus are not inhibited by EDTA) but are inhibited by sodium borohydride, NaBH4, in the presence of substrate (see A Deeper Look, page 622). Class II aldolases are produced mainly in bacteria and fungi and are not inhibited by borohydride, but do contain an active-site metal (normally zinc, Zn ) and are inhibited by EDTA. Cyanobacteria and some other simple organisms possess both classes of aldolase. 

In general, imines are too reactive to be used to protect carbonyl groups. In a synthesis of juncusol, however, a bromo- and an iodocyclobexylbnine of two identical aromatic aldehydes were coupled by an Ullmann coupling reaction modified by Ziegler. The imines were cleaved by acidic hydrolysis (aq. oxalic acid, THE, 20°, 1 h, 95% yield). Imines of aromatic aldehydes have also been prepared to protect the aldehyde during ring metalation with. -BuLi. ... 

C. The structure, which involves two bridging carbonyl groups as shown in Fig. 26.8a, can perhaps be most easily rationalized on the basis of a bent Co-Co bond arising from overlap of angled metal orbitals (d sp hybrids). However, in solution this structure is in equilibrium with a second form (Fig. 26.8b) which has no bridging carbonyls and is held together solely by a Co-Co bond. 

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