Cobalt complex compounds Subject

Chiral salen chromium and cobalt complexes have been shown by Jacobsen et al. to catalyze an enantioselective cycloaddition reaction of carbonyl compounds with dienes [22]. The cycloaddition reaction of different aldehydes 1 containing aromatic, aliphatic, and conjugated substituents with Danishefsky s diene 2a catalyzed by the chiral salen-chromium(III) complexes 14a,b proceeds in up to 98% yield and with moderate to high ee (Scheme 4.14). It was found that the presence of oven-dried powdered 4 A molecular sieves led to increased yield and enantioselectivity. The lowest ee (62% ee, catalyst 14b) was obtained for hexanal and the highest (93% ee, catalyst 14a) was obtained for cyclohexyl aldehyde. The mechanism of the cycloaddition reaction was investigated in terms of a traditional cycloaddition, or formation of the cycloaddition product via a Mukaiyama aldol-reaction path. In the presence of the chiral salen-chromium(III) catalyst system NMR spectroscopy of the crude reaction mixture of the reaction of benzaldehyde with Danishefsky s diene revealed the exclusive presence of the cycloaddition-pathway product. The Mukaiyama aldol condensation product was prepared independently and subjected to the conditions of the chiral salen-chromium(III)-catalyzed reactions. No detectable cycloaddition product could be observed. These results point towards a [2-i-4]-cydoaddition mechanism. 

Gibson and co-workers have introduced a well-designed latent cyclobutadiene moiety. Compound 49 reacts with a phenylethyne-cobalt complex to give PKR product 50 as a single diastereomer that resulted from the reaction at the less sterically hindered site, and 50 was subjected to the retro-Diels-Alder reaction at 205 °G under a vacuum of 6 torr to give 51 (Equation (23)). ... 

The word cluster in this section will refer to complexes of cobalt containing three or more metals for which there is, moreover, evidence for the existence of metal-metal bonds in the complex. In addition, for such compounds to be reported in this section, the otganometallic nature of the cluster (the direct interaction between one of the cobalt atoms and at least one carbon atom) must be present. In fact, purely inorganic cobalt clusters became more numerous until recently. Some examples will be described at the end of this section however, these compounds will not be coveted in any comprehensive fashion. Polynuclear clusters, which contain other metal atoms associated to cobalt, are the subjects of another chapter of this work. 

Perfluoroalkyl or -aryl halides undergo oxidative addition with metal vapors to form nonsolvated fluonnated organometallic halides and this topic has been die subject of a review [289] Pentafluorophenyl halides react with Rieke nickel, cobalt, and iron to give bispentafluorophenylmetal compounds, which can be isolated in good yields as liquid complexes [290] Rieke nickel can also be used to promote the reaction of pentafluorophenyl halides with acid halides [297] (equation 193)... 

Reaction systems containing cobalt and nickel were characterized by the production of flocculent precipitates of compounds other than hydroxides in the presence of all thiols, except for thiophenol and tert-butanethiol. Samples of these complexes produced from the ethanethiol system were washed, dried, and subjected to microanalysis. For nickel, the precipitate could be separated into two fractions by extracting with... 

Jeong and co-workers utilized a cobalt-alkyne complex to enhance enantioselectivity of the addition of bis (homoallyl)zinc to propargyl aldehydes 68 by the exaggeration of steric environment. The reaction provided optically enriched propargyl alcohol 69 in the presence of a chiral ligand and titanium tetra(isopropoxide) in excess. Adduct 69 was subjected to PKR to yield optically enriched bicyclic compounds 70 (Equation (39)). ... 

In their first publication on this subject,59 Werner and Miolati showed that the molecular conductances (fx) of coordination compounds decreased as successive molecules of ammonia were replaced by acid residues (negative groups or anions). For cobalt(III) salts, they found that fi for luteo salts (hexaammines) > fi for purpureo salts (acidopentaammines) > /t for praseo salts (di-acidotetraammines). The conductance fell almost to zero for the triacidotriammine Co(N02)3-(NH3)3 and then rose again for tetracidodiammines, in which the complex behaved as an anion. By such measurements, Werner and Miolati determined the number of ions in complexes of cobalt(III), platinum(II) and platinum(IV). They not only found support for the coordination theory, but they also elucidated the process of dissociation of salts in aqueous solution and followed the progress of aquations. 

Much more important commercially are the 2 1 chromium(III) and 2 1 cobalt(III) complexes of tridentate azo compounds, which find a wider application, particularly as dyestuffs for wool, polyamide fibres and leather. These have been the subject of reviews23 24 which discuss their dyeing properties in detail. The patent literature on metal complex dyes of these types is vast but since this relates principally to the achievement of specific, desirable technical effects by appropriate substitution of the azo compounds it will not be considered in detail here. Rather will the emphasis be placed upon those aspects of dyestuffs of this type which are of general interest in the context of their coordination chemistry and, more particularly, on those areas where uncertainties exist or conflicting results have been reported. 

These complexes, all of which contain cobalt within a macrocyclic ligand and an axial cobalt-carbon bond, have been found to be photosensitive and have been the subject of numerous photochemical studies. Space does not permit a detailed summary of all the studies which have been conducted on these classes of compounds, and we present here only a general summary of the various observations and discuss pertinent articles from the most recent literature. The reader is referred to an excellent review of the subject by Koerner von Gustorf et al. 108) which presents a detailed discussion of reports that appeared prior to 1975. 

The preparation of bis(bipyridyl) (702) and bis(phenanthroline) cobalt(III) complexes (576) has been the subject of a number of papers. Interest centers on the possibility of cis-trans isomerism in these complexes, since it would seem that the close approach of the 6,6 -(bipyridyl) and 2,9-(phenanthroline) protons in the trans complex would make this stereochemistry unattractive for central ions such as co-balt(III), rhodium(III), or iridium(III). Cis complexes are well established, but a violet compound claimed to be anionic cobalt(II) species (21, 573, 591). 

Only a few homo- mid heterometallic dodecacarbonyl compounds have been the subject of variable-pressure studies for various reasons insolubility (Ir4(CO)i2), intensity distortions in the NMR spectra (Co4(CO)i2 [39] and most other systems containing cobalt [40]), two parallel fluxional processes with similar rates (M3(CO)i2-x(NCCH3) r (M = Ru, jc = 1,2, 3 M = Os, x = 1, 2 [41], complex mixture of conformers (Fe3(CO)i2 [42]), or static behaviour (OS3(CO),2). 

The chemistry of silicon, germanium, and tin transition metal compounds has been the subject of several reviews (12, 180). Optically active silyl ligands have been introduced in a transition metal complex by reaction of chiral functional organosilanes. However chiral silyl ligands containing complexes are limited to a few metal centers we shall discuss in turn iron, cobalt, platinum, and manganese complexes. 

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