Active sites, coordinatively unsaturated

We have proposed (12, 21) that the active sites which develop during activation are coordinatively unsaturated surface ions formed by loss of water. This idea is, of course, not new, but advances in the theory of inorganic chemistry permit us to employ the concept with greater pre-... 

The active acid sites in ZSM-5 can also be characterized spectroscopically in a less direct manner by observing their interaction with basic molecules. For example, the infrared spectrum of chemisorbed pyridine shows bands characteristic of the pyridinium cation formed by reaction with Brtfnsted (protonic) acid sites, and pyridine coordinated to Lewis acid sites (coordinatively unsaturated A1 ). Figure 3(a) shows the spectrum of pyridine chemisorbed in a freshly activated ZSM-5, compared with the corresponding spectrum in Figure 3(b) of pyridine in the same zeolite partially coked after methanol conversion (ref. 

Although Z.N. catalysts are very sensitive to polar substituents which tend to clock active sites, coordination polymerization by modified complexes is of course not limited to unsaturated hydrocarbons. A few examples are discussed hereafter which have put in evidence interesting new concepts. 

Recenl work has defined more carefully ihe nature of active sites. Metal surfaces are thought to contain three main types of sites terraces, ledges (or steps) and kinks, which correspond to one, two. and three coordinatively unsaturated sites of organometallic chemistry. These sites display differing activities toward saturation, isomerization, and CKChiingQ 7 J0,68 JO 1.103,104,105). 

Class 111-type behavior is the consequence of this impossibihty to create step-edge-type sites on smaller particles. Larger particles wiU also support the step-edge sites. Details may vary. Surface step directions can have a different orientation and so does the coordinative unsaturation of the atoms that participate in the ensemble of atoms that form the reactive center. This wiU enhance the activation barrier compared to that on the smaller clusters. Recombination as well as dissociation reactions of tt molecular bonds will show Class 111-type behavior. 

All mechanisms proposed in Scheme 7 start from the common hypotheses that the coordinatively unsaturated Cr(II) site initially adsorbs one, two, or three ethylene molecules via a coordinative d-7r bond (left column in Scheme 7). Supporting considerations about the possibility of coordinating up to three ethylene molecules come from Zecchina et al. [118], who recently showed that Cr(II) is able to adsorb and trimerize acetylene, giving benzene. Concerning the oxidation state of the active chromium sites, it is important to notice that, although the Cr(II) form of the catalyst can be considered as active , in all the proposed reactions the metal formally becomes Cr(IV) as it is converted into the active site. These hypotheses are supported by studies of the interaction of molecular transition metal complexes with ethylene [119,120]. Groppo et al. [66] have recently reported that the XANES feature at 5996 eV typical of Cr(II) species is progressively eroded upon in situ ethylene polymerization. 

The active species of the metallocene/MAO catalyst system have now been established as being three-coordinated cationic alkyl complexes [Cp2MR] + (14-electron species). A number of cationic alkyl metallocene complexes have been synthesized with various anionic components. Some structurally characterized complexes are presented in Table 4 [75,76], These cationic Group 4 complexes are coordinatively unsaturated and often stabilized by weak interactions, such as agostic interactions, as well as by cation-anion interactions. Under polymerization conditions such weak interactions smoothly provide the metal sites for monomers. 

BLM transport systems for ferrioxamine B were also devised based on first coordination shell recognition via ternary complex formation utilizing vacant coordination sites on the Fe(III) center (Fig. 29) (199). The tetra-coordinated substrate complex selectively transported was partially dechelated diaqua-ferrioxamine B and coordinately unsaturated di-hydroxamato iron(III) complexes, which utilized a hydrophobic membrane bound bidentate chelator as a carrier for selective transport. Active transport for these systems was accomplished using a pH gradient (199). 

Therefore, the data indicate that Co-Mo-S can be considered as a M0S2 structure with Co atoms located in edge positions. As discussed below, these Co atoms play a direct role in the catalysis. Furthermore, it is generally accepted that the HDS reaction involves adsorption on sulfur vacancies. The low sulfur coordination number (large coordinative unsaturation) estimated from the Co EXAFS may, in fact, reflect that active sites (vacancies) are associated with the Co atoms. 

The anion vacancy sites have acid properties. As stated above, the catalytic activity and the hydrogenolytic behavior correlated with the acid properties of the catalyst, as well as the extent of reduction. Therefore, the adsorption of an aryl group will occur on the coordinatively unsaturated molybdenum sites generated during reduction. According to the reaction scheme for the hydrogenation of ethylene over a reduced MoOj-AljOj catalyst, ethylene becomes it-bonded at a second vacant ligand position of a coordinatively unsaturated Mo species and inserts to form the [Pg.267]

Finally, the active sites for the hydrogenolysis of asym DAM are Mo(IV) species that originated from the reduction of the octahedral Mo(VI) species. The adsorption of the aryl group occurs on the coordinatively unsaturated molybdenum sites, which have acidic properties this fact, in turn, leads to the reaction mechanism of the interaction between the active species and the substrates. 

The coordinatively unsaturated hydride complex is proposed to be active site in the hydrogenation of olefins under mild conditions [24]. 

Alkanes can also be activated by oxidative addition of coordinatively unsaturated organo-metallic reagents. In the presence of carbon monoxide, C—C bond formation can ensue, e.g., the conversion of pentane to hexanal7. Note that this method, highly selective for primary sites, is complementary to the radical-based chemistry outlined above. 

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