Carbonyl clusters oxidation

The main synthetic route to high nuclearity metal carbonyl clusters involves a condensation process (/) a reaction induced by coordinatively unsaturated species or (2) a reaction between coordinatively saturated species in different oxidation states. As an example of (/), Os2(CO)22 can be condensed to form a series of higher coordinated species (89). 

A general property of these carbonyl clusters is their tendency to behave as electron sinks , and their redox chemistry is extensive. [OsioC(CO)24]" has been characterized in no less than five oxidation states (n = 0-4) though admittedly this is exceptional. 

Abstract This review is a summary of supported metal clusters with nearly molecular properties. These clusters are formed hy adsorption or sirnface-mediated synthesis of metal carbonyl clusters, some of which may he decarhonylated with the metal frame essentially intact. The decarhonylated clusters are bonded to oxide or zeolite supports by metal-oxygen bonds, typically with distances of 2.1-2.2 A they are typically not free of ligands other than the support, and on oxide surfaces they are preferentially bonded at defect sites. The catalytic activities of supported metal clusters incorporating only a few atoms are distinct from those of larger particles that may approximate bulk metals. 

Supported metal carbonyl clusters are alternatively formed from mononuclear metal complexes by surface-mediated synthesis [5,13] examples are [HIr4(CO)ii] formed from Ir(CO)2(acac) on MgO and Rh CCOlie formed from Rh(CO)2(acac) on y-Al203 [5,12,13]. These syntheses are carried out in the presence of gas-phase CO and in the absence of solvents. Synthesis of metal carbonyl clusters on oxide supports apparently often involves hydroxyl groups or water on the support surface analogous chemistry occurs in solution [ 14]. A synthesis from a mononuclear metal complex precursor is usually characterized by a yield less than that attained as a result of simple adsorption of a preformed metal cluster, and consequently the latter precursors are preferred when the goal is a high yield of the cluster on the support an exception is made when the clusters do not fit into the pores of the support (e.g., a zeolite), and a smaller precursor is needed. 

Synthesis of metal carbonyl clusters on oxide surfaces (followed by extraction into a solvent and workup) is occasionally a more convenient and efficient method for preparation of a metal carbonyl cluster than conventional solution chemistry. This synthetic strategy offers the green chemistry advantage of minimizing solvent use, as the reaction often occurs in the absence of solvent. 

The field of surface-mediated synthesis of metal carbonyl clusters has developed briskly in recent years [4-6], although many organometallic chemists still seem to be unfamiliar with the methods or consider themselves ill-equipped to carry them out. In a typical synthesis, a metal salt or an organometallic precursor is brought from solution or the gas phase onto a high-area porous metal oxide, and then gas-phase reactants are brought in contact with the sample to cause conversion of the surface species into the desired products. In these syntheses, characteristics such as the acid-base properties of the support influence fhe chemisfry, much as a solvenf or coreactant influences fhe chemisfry in a convenfional synfhesis. An advanfage of... 

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. 

The exceptional renewed interest in supported gold catalysts leads us to mention here a few recent examples of the formation of in situ gold carbonyl species from supported gold that can be related to the preparation of supported Au nanoclusters [53-55]. On the other hand, bimetallic carbonyl cluster salts of [Au4Fe4(CO)i,5] and [AuFe4(CO)i,5] have been used recently in the preparation of Au/Fe0,t/Ti02 catalysts for the total oxidation of dichlorobenzene and toluene [56]. 

Oxidation of the tetracobalt clusters is made easier by the successive phosphine substitution. The anion radical derived from the 0/ — 1 redox couple of the cluster is substitution-ally labile. The cyclic voltammetric pattern of tetracobalt carbonyl cluster is shown in Figure 3. 

Tetranuclear clusters Pt4(CO)5L4 and Pt4(CO)5L3 have been prepared from the reaction of CO on the trinuclear species.336,347 For tetrametallic compounds examples are found with Pt2Mo2, Pt2Co2 and Pt2M2 (M = Cr, Mo, w).348,349 These latter complexes show an irreversible two-electron reduction leading to the rupture of the metallic core into identified fragments. These complexes are of the type [PtM(jU3-CO)(ji2-CO)2Cp(PPh3)]2, and the first two oxidation waves indicate one-electron processes.349 A tetrametallic carbonyl cluster PtOs3(fi-H)2(CO)io(PR3) has also been characterized.350... 

The first class of reactions, direct transfer of an oxygen atom from the oxidant to carbon monoxide, has not been commonly observed as a reaction catalyzed by metal complexes in solution. One example, derived from a preparative procedure developed to substitute carbonyls with other ligands (90), is the reaction of trimethylamine oxide, Me3NO, with carbonyl clusters such as Os3(CO)12 in the presence of excess CO. The net reaction is shown as (27). 

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