Disodium tetracarbonylferrate

PORONCOMPOUNDS - BORON OXIDES, BORIC ACID AND BORATES] (Vol 4) Disodium tetracarbonylferrate [59733-73-2]... 

Anhydrides, both aliphatic and aromatic, as well as mixed anhydrides of carboxylic and carbonic acids, have been reduced to aldehydes in moderate yields with disodium tetracarbonylferrate Na2Fe(CO)4. Heating a carboxylic acid, presumably to form the anhydride, and then reaction with Na/EtOH leads to the aldehyde. 

Caution Iron pentacarbonyl, carbon monoxide, and methyl iodide are highly toxic, consequently all parts of this procedure should be carried out in a well-ventilated hood. Iron pentacarbonyl is easily recognized by its musty odor. Since disodium tetracarbonylferrate is... 

Disodium tetracarbonylferrate sesquidioxanate Ferrate(2-), tetra-carbonyl (1,4-dioxane-O )-, disodium (9) (57398-59-1)... 

The initial reaction between the alkyl halide (or p-toluenesulfonate) and disodium tetracarbonylferrate behaves as a typical Sn2-type substitution. Thus this step proceeds smoothly with primary and secondary reactants, but the tertiary analogs fail... 

Azolides are also capable to acylate anionic metal carbonyl compounds. For instance, disodium tetracarbonylferrate as well as the corresponding ruthenium and osmium compounds can be formylated with formylimidazole in the presence of boric acid methyl ester ... 

Nonacarbonyldiiron in the presence of activated zinc as well as disodium tetracarbonylferrate have both been utilized to dechlorinate dimethyl cispransjransA,2,3,4-tetrachlorocyclobutane-1,2-dicarboxylate (41), which leads to [dimethyl l,2,3,4- 7-l,3-cyclobutadiene-l,2-dicarboxy-latejiron tricarbonyl (42) in 1 and 35-40% yield, respectively.15 As a result of the better leaving tendency of the bromide anion, the yield of 42 can be improved to 70% by reaction of the analogous dibromide with nonacarbonyldiiron in dimethylformamide.16 In another experiment, debromination with activated zinc in tetrahydrofuran converts cyclobutane-1,2-di-carboxylate 43 to cyclobutene-1,2-dicarboxylate 44 in 58% yield.15... 

When aldehydes, with or without a hydrogen, are treated with aluminum ethoxide, one molecule is oxidized and another reduced, as in 9-69, but here they are found as the ester. The process is called the Tishchenko reaction. Crossed Tishchenko reactions are also possible. With more strongly basic alkoxides, such as magnesium or sodium alkoxides, aldehydes with an a hydrogen give the aldol reaction. Like 9-69, this reaction has a mechanism that involves hydride transfer.751 The Tishchenko reaction can also be catalyzed752 by ruthenium complexes.753 by boric acid,754 and, for aromatic aldehydes, by disodium tetracarbonylferrate Na2Fe(CO)4,755 OS I, 104. 

One of the most important reagent equivalents of the donor formyl synthon is 1,3-dithiane (see Chapter 1, p. 21). However the use of this reagent equivalent is not widely found for the synthesis of simple aldehydes since other methods may be economically more appropriate. An example of specific formylation by the use of 1,3-dithiane is illustrated in Expt 6.66. Disodium tetracarbonylferrate(n)... 

Addition of nucleophiles to a carbon monoxide ligand of pentacarbonyliron provides anionic acyliron intermediates which can be trapped by electrophiles (H+ or R—X) to furnish aldehydes or ketones [18]. However, carbonyl insertion into alkyl halides using iron carbonyl complexes is more efficiently achieved with disodium tetracarbonylferrate (Collman s reagent) and provides unsymmetrical ketones (Scheme 1.2) [19, 20]. Collman s reagent is extremely sensitive towards air and moisture, but offers a great synthetic potential as carbonyl transfer reagent. It can be prepared by an in situ procedure starting from Fe(CO)5 and Na-naphthalene [20]. 

REDUCTION, REAGENTS Bis(triphenyl-phosphine)copper tetrahydroborate. Borane-Pyridine. Calcium-Methylamine/ ethylenediaminc. Chlorobis(cyclopenta-dienyl)tetrahydroboratozirconium(IV). Chromium(II)-Amine complexes. Copper(0)-lsonitrile complexes. 2,2-Dihydroxy-l, 1-binaphthyl-Lithium aluminum hydride. Di-iododimethylsilane. Diisobutyl-aluminum 2,6-di-/-butylphenoxide. Diisobutyl aluminum hydride. Dimethyl sulfide-Trifluoroacetic anhydride. Disodium tetracarbonylferrate. Lithium-Ammonia. Lithium-Ethylenediamine. Lithium bronze. Lithium aluminum hydride. Lithium triethylborohydride. Potassium-Graphite. 1,3-Propanedithiol. Pyridine-Sulfur trioxide complex. 

Disodium tetracarbonylferrate, 205-207 Disodium tetrachloropalladate, 207 Disodium tetracyanonickelate, 207 N,N -Disuccinimidyl carbonate, 208 cndo-Disulfides, 435-436... 

The reaction of l-chloro-17/-phosphirene 4 with disodium tetracarbonylferrate leads to selective formation of monocomplexed bi-l/7-phosphirene 6, which is converted into the doubly complexed species 7 upon treatment with diiron nonacarbonyl (Scheme 4) <2001EJI2067>. 

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