Larger carbonyl clusters

This reaction is diffusion controlled in solid CO. The binuclear carbonyl is unstable and even at these low T decomposes to Ag2 or higher clusters. Similarly, Au forms Au(CO)[ or 2, which does not dimerize. However, Cu cocondensed with CO and Ar forms compounds Cu (CO) (n = 1-4), which after warming to 35 K decompose to larger Cu carbonyl clusters of indeterminate composition, the IR spectra of which resemble CO chemisorbed onto bulk Cu. 

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. 

In many instances, the formation of inactive dimers from active, monomeric catalytic species is observed during catalysis. When weak or unstable ligands are used, even larger rhodium carbonyl clusters like Rh4(CO)i2 and Rh5(CO)i5 can be observed [42-44]. The formation of dimers is often a reversible equilibrium (Scheme 6.2). This only leads to a reduction in the amount of catalyst available and does not kill the catalyst. One of the first examples was the formation of the so-called orange dimer from HRh(PPh3)3CO, already reported by Wilkinson [45]... 

The v(CO)t- slopes for saturated CO adlayers at both single-crystal and polycrystalline Pt-nonaqueous interfaces are noticeably smaller than those for the corresponding solvated Pt carbonyl clusters. These differences are explained as being chiefly due to larger effective... 

The compound K2 [Rh6(CO)15C] is a yellow powder. It is sensitive to air both in the solid state and in solution and is quite soluble in water, methanol, ethanol, acetone, THF, and acetonitrile. The salts of other cations can be obtained by metathesis, in water for the cesium salt and in methanol for the larger tetra-alkylammonium or phosphonium cations. The tetraethylammonium salt is sparingly soluble in THF, whereas the benzyltrimethylammonium and bis-(triphenylphosphine)imminium salts are soluble. All of these salts are soluble in acetone and acetonitrile. The yellow solution of the potassium salt in THF shows characteristic IR bands at 2040 (vw), 1990 (vs), 1885 (vw), 1845 (s), 1830 (sh, m) 1815 (sh, br) and 1775 (vw, br) cm-1. The IR spectral band shapes depend on solvents and cations. The oxidation of K2 [Rh6(CO)i5C] with iron-(III) ammonium sulfate in water under carbon monoxide leads to the octa-nuclear carbido carbonyl cluster Rhg(CO)i9C,6 whereas under nitrogen RhntCO sQ7 or [H30] [Rhls(CO)28C2]8 is obtained. 

Metal triangles, tetrahedra, and octahedra form the basic building blocks of transition metal carbonyl clusters. The smaller clusters with between three and six metal atoms often adopt these pseudo-spherical deltahedral geometries, but as the nucle-arity of the cluster increases, condensed structures, built up from the smaller poly-hedra by vertex-, edge-, or face-sharing, tend to be favored in preference to the larger spherical deltahedra based on the Platonic and Archimedean solids. In general, this is in contrast to the structures foimd in borane chemistry. 

Many main-group atoms have been found to occupy interstitial positions in transition metal carbonyl clusters and there are now examples of H, B, C, N, O, Si, P, S, Ge, As, Sn, and Sb atoms being encapsulated, either fully or partially, within a metal skeleton. In general, the size limitations associated with the internal cavity of the cluster determine the type of atom which can occupy the interstitial site. Although the radius of the cavity is determined primarily by the nuclearity and geometry of the cluster, the size of the metal atoms relative to that of the interstitial atom is a critical factor, and clusters with larger cavities are observed as the ratio of the covalent radius of the main-group atom to that of the transition metal atoms increases. 

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