Metal clusters molybdenum

Table 5 shows HDS product distributions over several catalysts prepared by using the molybdenum-nickel cluster 2. Sulfur content in decane was adjusted to 5.0 wt% in these experiments. MoNi/NaY was found to be more active than MoNi/Al203. It is to be noted that during the high temperature pretreatment the original cluster structure would have been changed. However, the high activity of the MoNi/NaY catalyst for benzothiophene HDS is probably due to the formation of active sites derived from this particular mixed metal cluster. 

Our work was initiated on the reduced ternary molybdenum oxides with the thought that the metal cluster electron count (MCE) should be variable for the Mo308 cluster units. Based on Cotton s previous molecular orbital treatment of such clusters (16) it appeared that MCE s from 6 to 8 could be accommodated, but it was not clear whether the seventh and eighth electrons would occupy bonding or antibonding orbitals with respect to the M-M interactions. We thus set about to determine this from structural data on suitable compounds. The attempted replacement of Zn2+ with Sc3+ to secure the compound ZntSc°Mo308 was conducted via the reaction shown in equation 1. 

The serendipitous discovery of this compound has proven to be extremely important to our visions of possibilities for new metal-metal bonded structures in reduced oxide phases. In retrospect it is amazing that oxide phases containing molybdenum in oxidation states less than 4+ were essentially unknown and certainly structurally uncharacterized. The existence of the previously mentioned series M2 Mo30q and LiM Mo303 should have been a tip-off to an extensive chemistry for metal-metal bonded molybdenum oxide systems. Indeed, subsequent work has revealed a plethora of new compounds all of which (where structure has been determined) feature strong metal-metal bonding in either discrete cluster units or extended chain arrays. 

TOF-SIMS images (Figs. 13.5 and 13.6) illustrate the ability to detect changes in the dispersion (uniform or presence of metal clusters) of the active phase in supported-oxide catalysts. Figure 13.5 shows nearly uniform distribution of molybdenum. The surface contamination with NH4+ ions coming from a precursor, which were not removed during the catalyst preparation process, is also observed. Cobalt clusters in the range of several micrometers are clearly visible in Fig. 13.6. 

The octahedral metal clusters that have long been familiar features of the lower halide chemistry of niobium, tantalum, molybdenum, and tungsten represent a category of cluster different from those so far considered in that their metal-metal bonding is best treated as involving four AO s on each metal 49, 133,144,165,178). 

The use of highly dispersed catalysts from soluble salts of molybdenum is another approach to the reduction of catalyst amount because of their excellent activity despite their higher price. Recently, metal carbonyl compounds, such as Fe(CO)5, Ru3(CO)i2, and Mo(CO)6 have been investigated as metal cluster catalysts. Preparation involved their deposition and decomposition on catalyst support surfaces (71-73). 

Thus far, dimensional reduction has not been applied in this way to any of the other parent solids listed in Table I. Of particular interest are systems that straddle the divide between the edge-bridged and face-centered octahedral geometries. Will reduced niobium-molybdenum halide mixtures simply disproportionate or will they lead to new mixed-metal clusters If the latter, then where does the crossover in cluster geometries occur An important factor in applying dimensional reduction is recognizing the variability in the stable electron counts within a particular cluster system. An extreme case occurs... 

Trinuclear clusters play an important role in the chemistry of molybdenum and tungsten. Deep red, isostructural clusters containing both [M03O4F9]3- (148, 149) and [W304F9]5 (149-151) are later additions to this family of simplest types of cluster species. Their basic structures conform to the fii-type of trinuclear electron-poor transition-metal clusters where the metals are in a distorted octahedral environment. 

Bolen, J.T., Cambasso, N., Muchmore, S.W., Morgan, T.V., and Mortenson, L. E. (1993) Structure and Environment of metal clusters of the nitrogenase molybdenum iron protein from Clostridium pasterianum, in Stiefel, E.I., Coucouvanis, D., and ewton, W.E. (eds.), Molibdenum Enzymes, Cofactors, and Model Systems, Am. Chem. Soc., Wahington, DC. 

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