Metal surface-mediated synthesis

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. 

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... 

In addition, surface-mediated synthesis results a powerful tool in the preparation of surface carbonyl species (homo- or heteronuclear) that are further precursors of supported, tailored metallic catalysts. 

Figure 15.1 Ordered nanoscale structures of mesoporous materials such as FSM-16 and HMM-1 (Et-HMM-1) as the silica and organosilica templates for surface-mediated synthesis of metal/alloy nanowires and nanoparticles.

Surface-Mediated Synthesis of Metal/Alloy Nanowires Using Mesoporous Templates... 

Other Surface-Mediated Synthesis of Metal Nanowires on Porous Membrane and Graphite Steps... 

Ni and Co or of oxophilic metals, for example. Re, is still poorly studied the surface-mediated synthesis of bimetallic carbonyl clusters is limited to a few examples the surface-mediated synthesis of metal compounds without carbonyl ligands has just begun with the silica-mediated synthesis of [RhH2(PMe3)4] by treatment of bis (allyl) rhodium with PMe3 followed by H2 [121] the silica-mediated synthesis of tantalum clusters has been investigated recently but the products were not extracted from the surface-for example, treatment of silica physisorbed Ta(CH2Ph)5 in H2 at 523 K for 20 h led to tri-tantalum clusters, as shown by EXAFS spectroscopy [122]. 

Gates, B. C., Surface-mediated synthesis of metal clusters. J. Mol. Catal. 86,95 (1994). 

Supported metal clusters are often prepared by (a) bonding of precursor metal carbonyl clusters followed by removal of carbonyl ligands attempting to maintain the metal clusters frame intact, (b) surface-mediated synthesis in which the supported... 

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. 

We have reviewed the state of the art of the synthesis and applications of metal/ alloy nanowires and nanoparticles by surface-mediated fabrication using different mesoporous silica templates. New nanoscale materials are appearing one after another by the use of many kinds of mesoporous materials as templates, and we are facing a rapid advance of this research field. So far, many studies have focused... 

I 76 Surface-Mediated Organometallic Syntheses Table 16.5 Traditional synthesis of Os metal carbonyl complexes and clusters in solution". 

PPG 425 has been used in the preparation of a range of benzaldehydes that were subsequently used in the solvent free synthesis of calix[4]resorcinarenes. The aldehydes are isolated in near quantitative yields by distillation from the PPG, which can be recycled. PPG has also been used in the indium metal mediated allylation of imines and sulfonylimines. Ultrasound was used for two reasons to clean the metal surface and to increase the solubility of the imine in PPG. The solvent was recycled three times, but a desire to develop an easier drying and recycling method was indicated. 

Adapted with permission from Wada S. Urano M, Suzuki H. The newborn surface of dull metals in organic synthesis bismuth-mediated solveht-free one-step conversion of nitroarenes to azoxy- and azoarenes. J Org Chem 2002 67 8254-7, Copyright 2002 American Chemical Society. 

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