Metal carbonyls reductive carbonylation

In atomization, a stream of molten metal is stmck with air or water jets. The particles formed are collected, sieved, and aimealed. This is the most common commercial method in use for all powders. Reduction of iron oxides or other compounds in soHd or gaseous media gives sponge iron or hydrogen-reduced mill scale. Decomposition of Hquid or gaseous metal carbonyls (qv) (iron or nickel) yields a fine powder (see Nickel and nickel alloys). Electrolytic deposition from molten salts or solutions either gives powder direcdy, or an adherent mass that has to be mechanically comminuted. 

Because transition metals even in a finely-divided state do not readily combine with CO, various metal salts have been used to synthesize metal carbonyls. Metal salts almost always contain the metal in a higher oxidation state than the resulting carbonyl complex. Therefore, most metal carbonyls result from the reduction of the metal in the starting material. Such a process has been referred to as reductive carbonylation. Although detailed mechanistic studies ate lacking, the process probably proceeds through stepwise reduction of the metal with simultaneous coordination of CO (90). 

Two techniques, electrochemical reduction (section IIl-C) and Clem-mensen reduction (section ITI-D), have previously been recommended for the direct reduction of isolated ketones to hydrocarbons. Since the applicability of these methods is limited to compounds which can withstand strongly acidic reaction conditions or to cases where isotope scrambling is not a problem, it is desirable to provide milder alternative procedures. Two of the methods discussed in this section, desulfurization of mercaptal derivatives with deuterated Raney nickel (section IV-A) and metal deuteride reduction of tosylhydrazone derivatives (section IV-B), permit the replacement of a carbonyl oxygen by deuterium under neutral or alkaline conditions. 

C-C bonds can be formed by reaction with alkyl iodides or more usefully by reaction with metal carbonyls to give aldehydes and ketones e.g. Ni(CO)4 reacts with LiR to form an unstable acyl nickel carbonyl complex which can be attacked by electrophiles such as H+ or R Br to give aldehydes or ketones by solvent-induced reductive elimination ... 

Bis ( -arene) metal complexes have been made for many transition metals by the AI/AICI3 reduction method and cationic species [M( j -Ar)2]"" " are also well established for n = 1, 2, and 3. Numerous arenas besides benzene have been used, the next most common being l,3,5-Mc3C6H3 (mesitylene) and CeMce. Reaction of arenas with metal carbonyls in high-boiling solvents or under the influence of ultraviolet light results in the displacement of 3CO and the formation of arena-metal carbonyls ... 

Metal-induced reductive dimerization of carbonyl compounds is a useful synthetic method for the formation of vicinally functionalized carbon-carbon bonds. For stoichiometric reductive dimerizations, low-valent metals such as aluminum amalgam, titanium, vanadium, zinc, and samarium have been employed. Alternatively, ternary systems consisting of catalytic amounts of a metal salt or metal complex, a chlorosilane, and a stoichiometric co-reductant provide a catalytic method for the formation of pinacols based on reversible redox couples.2 The homocoupling of aldehydes is effected by vanadium or titanium catalysts in the presence of Me3SiCl and Zn or A1 to give the 1,2-diol derivatives high selectivity for the /-isomer is observed in the case of secondary aliphatic or aromatic aldehydes. 

The reactions of nucleophilic reagents with cationic and uncharged metal carbonyl complexes have received much attention in the past, and it is not surprising that these studies have now been extended to isocyanide metal complexes. Different products in these reactions can arise by three general routes these include ligand substitution, reactions involving attack at a ligand, and reduction of the metal complex. All have been observed in reactions with metal isocyanide complexes. 

The most intensive development of the nanoparticle area concerns the synthesis of metal particles for applications in physics or in micro/nano-electronics generally. Besides the use of physical techniques such as atom evaporation, synthetic techniques based on salt reduction or compound precipitation (oxides, sulfides, selenides, etc.) have been developed, and associated, in general, to a kinetic control of the reaction using high temperatures, slow addition of reactants, or use of micelles as nanoreactors [15-20]. Organometallic compounds have also previously been used as material precursors in high temperature decomposition processes, for example in chemical vapor deposition [21]. Metal carbonyls have been widely used as precursors of metals either in the gas phase (OMCVD for the deposition of films or nanoparticles) or in solution for the synthesis after thermal treatment [22], UV irradiation or sonolysis [23,24] of fine powders or metal nanoparticles. 

Coordination compounds of d10, diamagnetic, Ir(-I) are very rare and are almost always synthesized via reduction of the parent Ir1 ds complex. The synthesis, characterization, and chemical properties of highly reduced metal carbonyl anions, including Ir, have been reviewed by Ellis in 1990.752... 

Metallic powders are made several different ways. They can be prepared by reducing salts in a stream of a reducing gas, such as hydrogen chlorides of metals are commonly used but oxides are used too. Thermal decomposition in a vacuum of metal carbonyls or metal salts of organic acids, such as formates, produces metal powders. Surface areas of such powders are around 1.5 m2/g. Powders can also be made from electrolytic reduction of salts in organic solvents and by atomization of the metal. 

The possible mechanisms which one might invoke for the activation of these transition metal slurries include (1) creation of extremely reactive dispersions, (2) improved mass transport between solution and surface, (3) generation of surface hot-spots due to cavitational micro-jets, and (4) direct trapping with CO of reactive metallic species formed during the reduction of the metal halide. The first three mechanisms can be eliminated, since complete reduction of transition metal halides by Na with ultrasonic irradiation under Ar, followed by exposure to CO in the absence or presence of ultrasound, yielded no metal carbonyl. In the case of the reduction of WClfc, sonication under CO showed the initial formation of tungsten carbonyl halides, followed by conversion of W(C0) , and finally its further reduction to W2(CO)io Thus, the reduction process appears to be sequential reactive species formed upon partial reduction are trapped by CO. 

The induction of steric effects by the pore walls was first demonstrated with heterogeneous catalysts, prepared from metal carbonyl clusters such as Rh6(CO)16, Ru3(CO)12, or Ir4(CO)12, which were synthesized in situ after a cation exchange process under CO in the large pores of zeolites such as HY, NaY, or 13X.25,26 The zeolite-entrapped carbonyl clusters are stable towards oxidation-reduction cycles this is in sharp contrast to the behavior of the same clusters supported on non-porous inorganic oxides. At high temperatures these metal carbonyl clusters aggregate to small metal particles, whose size is restricted by the dimensions of the zeolitic framework. Moreover, for a number of reactions, the size of the pores controls the size of the products formed thus a higher selectivity to the lower hydrocarbons has been reported for the Fischer Tropsch reaction. 

Metal carbonyls in a low oxidation state are able to induce the carbonylative transformation. Reductive carbonylation of the gem-dibromocyclopropanes 150 is realized by treatment with nickeltetracarbonyl in an alkanol to give the alkyl cyclopropanecarboxylates 151 with reduction of another bromide [79], Amines, phenol, and imidazole can also be used instead of alcohols. (Scheme 53)... 

In such a sequence the first complex incorporating the elements H, C, and O is a metal formyl species in Section II,A we describe the preparation and properties of such complexes. In Section II,B, stoichiometric reductions of both metal carbonyl and metal acyl species are presented and in Section II,C, homogeneous CO/H2 conversion catalysts are discussed. 

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