Sodium naphthalenide oxidation

Sn2 addition 413 Sn2 displacement 215 Sn2 lactone opening 412 ff. sodium bis(2-methoxyethoxy)-aluminium hydride see Red-Al sodium chlorite 516 - oxidation 772 sodium hypochlorite 550 f. sodium naphthalenide 739 f. sodium trimethoxyborohydride 390 SOMO 409... 

The monomeric carbonyl complexes of d M1 isolated so far are mainly the seven-coordinated [MX(CO)2(dmpe)2] compounds (M = Nb, X = Cl, Br, N3 697 M = Ta, X = H, Cl, Br, CN, Me, Et, Pr ) (53) has been obtained by reduction of [TaCl2(dmpe)2] with one equivalent of sodium naphthalenide under CO the other tantalum derivatives were generally prepared by oxidative additions to [Ta(CO)2(dmpe)2] formed in situ by reduction of (53 Scheme 10). The niobium analogs were formed by reductive carbonylation of [NbCU(dmpe)2].698... 

In addition to the procedure given here for the oxidation of tert-octylamine to nitroso-tert-octane,2 the oxidation may be carried out with m-chloroperoxybenzoic acid or with a solution of peroxyacetic acid in ethyl acetate.4 The lead dioxide oxidation of alkyl hydrazines to alkyl radicals appears to have general application. In addition to tert-butylhydrazine, various secondary alkylhydrazines (e.g., bornylhydrazine and menthylhydrazine) have been used to good effect. The reduction of tri-tert-alkylhydroxyl amine to the di-tert-alkylamine has also been achieved with sodium in ammonia but the insolubility of the hydrophobic substrate makes this procedure difficult. The use of sodium naphthalenide gives higher yields and is more reproducible. 

Reduction of [Mo(CO)2(bpy)2] using sodium amalgam or sodium naphthalenide gives paramagnetic [Mo(CO)2(bpy)2] in dimethoxyethane (81JOM(218)C31). Oxidation of [Mo(CO)2(bpy)2] using silver tetrafluoroborate in acetonitrile or aluminum chloride in methylene chloride and followed by sodium tetrafluoroborate gives... 

The remarkable hexanuclear complex [ NiCp ] (81), prepared by the sodium naphthalenide reduction of nickelocene, undergoes an extensive series of reversible one-electron transfer reactions cyclic voltammetry shows waves relating the six species [ NiCp 6] (Z = -2 to 3). Chemical oxidation of 81, with Ag, gave the monocation whose structure shows only a small tetragonal distortion from the octahedral array of nickel atoms in the neutral precursor (198). 

Electron-transfer to monomer is not the only mode of initiation by radical-anions, although it is unique for non-polar monomers. With some polar monomers, especially cyclic ones, the initiation resembles protonation. For example, the reaction of sodium naphthalenide with ethylene oxide follows the route (9)... 

Related anchored l,l,3,3-tetraphenyl-2-oxa-l,3-diphospholanium bis-triflate (39) has been prepared by reaction of brominated poly(styrene-co-divinylbenzene) resin 38 with the phosphorous anion generated from l,2-bis(diphenylphosphino)ethane and sodium naphthalenide followed by further oxidation and reaction with triflic anhydride (Scheme 7.13) [55]. This supported reagent has also been employed, to a lesser extent than 37, for the formation of esters and amides by reaction of carboxylic acids with primary alcohols and amines, respectively. 

Reduction-decyanation. wc-Cyanohydrins can be converted to alkenes by conversion to a methylthiomethyl ether followed by oxidation to the sulfone. Reduction of this derivative with sodium naphthalenide results in an alkene... 

A variety of clusters has been isolated from the reaction of [NiCp2] with sodium naphthalenide and amongst these is the unusual deep red octahedral [NigCpa] cluster that can be oxidized to [NieCpe]" both have nearly identical geometries. 

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