Carbonyl clusters with higher

Although anionic species with nickel in the oxidation state -I have been postulated, such as [Ni2(CO)6]2, these have not been confirmed. Nickel does, however, form a number of anionic carbonyl clusters with higher nuclearity, e.g., [Ni5(CO)l2]2-, in which the metal carries a partial negative charge. 

In some cases the basic amorphous oxide surface and zeolite matrix produces selected polynuclear carbonyl metal clusters with higher yields and higher selectivity than analogous inorganic syntheses in solution (Section VI,A). 

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. 

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. 

Addition of either nucleophilic or electrophilic metallic species can result in the capping of triangular- or square-metal faces in carbonyl clusters. These redox reactions provide high yield syntheses of higher nuclearity clusters and somewhat resemble surface reconstruction on metals. With a few examples,... 

Even though qualitative bonding descriptions of metal atom clusters up to six or seven atoms can be derived and in some cases correlated with structural detail, it is clear that most structures observed for higher clusters cannot be treated thus. Nor do the structures observed correlate with those observed for borane derivatives with the same number of vertices. Much of borane chemistry is dominated by the tendency to form structures derived from the icosahedron found in elemental boron. However, elemental transition metals possess either a close-packed or body-centered cubic arrangement. In this connection, one can find the vast majority of metal polyhedra in carbonyl cluster compounds within close-packed geometries, particularly hexagonal close-packing. 

The vibrational spectra at temperatures lower than 600 K are dominated by CO adsorbed on atop sites. At higher temperatures, atop CO is absent. The three bands observed were assigned to metal carbonyl clusters (2050 cm ), CO on oxidized Pt (2130 cm ), and CO2 (2240 cm ). The rate of CO oxidation at T > 600 K increased linearly with the intensity of the 2050... 

One of the conclusions of this study is that the first ligand substitution proceeds with a much higher coulombic efficiency than the second one, simply because of the increasing bulk at the metal center [317], This trend was known from previous studies of carbonyl substitution by phosphanes in transition-metal carbonyl clusters catalyzed by benzophenone radical anion [318, 319]. In such a case, selective ETC catalysts may be designed as a function of the required exergonicity of the desired initiation step [317]. 

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