Lithium ferrate

An experimental procedure for the conversion of iron(II) phthalocyanine into lithium methyl-(phthalocyanine)ferrate(II) can be found in Houben-Weyl, Vol. 13/9a, p 228. For analogous reactions involving cobalt, see Houben-Weyl, Vol. 13/9b, pp 55, 87. 

Alkyl (or phenyl) lithium formed with iron pentacarbonyl in situ lithium acyl-tetracarbonyl ferrates, Li[RCOFe(CO)4], which with iodonium salts afforded aryl ketones (48-85%) [41]. 

Strontium perferrate, SrFe04, is obtained 4 by double decomposition of the potassium salt and a saturated, neutral solution of strontium bromide. The precipitate is washed with alcohol and ether. Obtained in this manner, the strontium ferrate is not pure, but contains admixed ferric oxide. It is deep red in colour, slightly soluble in water, and readily decomposed by acids. It is useful for preparing aqueous solutions 4 of the perferrates of the less common alkali metals—lithium, rubidium, caesium—of calcium and magnesium. 

FeLi02 (s) LiFe02 (s) Lithium Ferrate(lll) FeLi02 (s) LiFe02 (s)... 

ALDEHYDES Bis(3-methyF2-butyl)-borane. Dichlorodicyanobenzoqui-none. I -Diphenylphosphonio-1 -meth-oxyincthyllithium. Disodium tetra-carhonyl ferrate. Grignard reagents. Lithium his(cthylcncdinxyhoryl)mcth-idc. Lithium mellioxyttriinethylsilyl)-... 

KETONES Lithium diisopropylamide. Nickel carbonyl. Sodium tetracarbonyl-ferrate(-II). Thallium(III) nitrate. 2,4,4,6-Tetramethyl-5,6-dihydro-l,3-(4 I)-oxazine. Triphenylmethyl hexafluorophosphate. y-KETONITRILES Sodium cyanide. (3-LACTONES Silver nitrate. y-LACTONES a-Chloro-N-cyclohexylpro-panaldoxime. 

The reduction of ferrous phthalocyanine with lithium benzophenone in tetrahydrofuran yields the solvated lithium phthalocyanine ferrate(I) (having one unpaired electron) and dilithium phthalocyanine ferrate(O) (diamagnetic) (340). The reduction of (LXXI) with alkaline sodium boro-hydride in methanol has also been studied 48). 

Acyltetracarbonylferrates, prepared from pentacarbonyliron and an alkyl-lithium, react with diaryliodonium salts to give ketones " pentacarbonyliron also reacts with alkyl halides in the presence of a phase-transfer catalyst to give the ferrate anion (38), which on addition of a second alkyl halide yields unsym-metrical ketones [equation (9)]/"... 

C4sH9gFeLi05, Lithium tetrakis[bis(t-butyl)methoxo]ferrate(III) bis(t-butyl)methanol, 46B, 1161... 

Figure 18.40 Layered structure of a sodium ferrate (III) as analogy of lithium cobaltite and lithium nickelite. (From Goodenough, Ref. 1.)...

Due to the low oxidation state of the metal in carbonyliron complexes and ferrates, these species can be applied for the reduction of various carbonyl compounds. Initially, these reagents have been applied in stoichiometric amounts. First examples describe the hydrogenation of a,p-unsaturated carbonyl compounds by carbonyl(hydrido)ferrate complexes to give saturated carbonyl compounds or saturated alcohols. Low valent iron species for the reduction of carbonyl compounds and imines can also be generated in situ from iron(II) chloride and lithium powder in the presence of 4,4 -di-rert-butylbiphenyl. Catalytic versions have been developed subsequently. Thus, pentacarbonyliron functions as a precatalyst for the hydrogenation of aldehydes and ketones in the presence of a tertiary amine as solvent (Scheme 4-322). The catalytically active system probably consists of (tetracarbonyl)(hydrido)ferrate and the protonated amine. ... 

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