Pt /ethylene

In the following we will concentrate on three important cases, i.e. CO oxidation on alkali doped Pt, ethylene epoxidation on promoted Ag and synthesis gas conversion on transition metals. We will attempt to rationalize the observed kinetic behaviour on the basis of the above simple rules. 

Likewise, mononuclear complexes of rhodium and platinum containing only one meth-ylenecyclopropane ligand are prepared by ligand exchange reactions of the Feist s esters with (acac)Rh(CO)2 and rra 5-Cl2(pyr)Pt(ethylene), giving complexes (acac)(CO)Rh(tF) and trans-C 2(pyr)FiL (L = cF, tF), respectively (equation 311). 

CSA relaxation on Pt can have unexpected influence on proton satellites. CSA relaxation increases with the square of the applied field. Olefinic NMR signal of fra s-Pt(ethylene)(2-carboxypyri-dine)Cl2 at 80 and 400 MHz showed severe CSA broadening of the Pt satellites at the higher field (Figure 21). 

The thermal reaction of Pt(ethylene)(PPh3)2 produces a dinuclear Pt(i) complex having a bridging PPh2 ligand and an orthometallated PPhs ligand 6 as one of the products Pt-G and Pt-P bonds are 209.4(8) and 267.7(5) pm, respectively. Oxidation by HgCl2 converts the complex to a dinuclear Pt(ii) complex. Complexes 7 are obtained by the reaction with Gu(i) and Ag(i) compounds. " ... 

Studies to determine the nature of intermediate species have been made on a variety of transition metals, and especially on Pt, with emphasis on the Pt(lll) surface. Techniques such as TPD (temperature-programmed desorption), SIMS, NEXAFS (see Table VIII-1) and RAIRS (reflection absorption infrared spectroscopy) have been used, as well as all kinds of isotopic labeling (see Refs. 286 and 289). On Pt(III) the surface is covered with C2H3, ethylidyne, tightly bound to a three-fold hollow site, see Fig. XVIII-25, and Ref. 290. A current mechanism is that of the figure, in which ethylidyne acts as a kind of surface catalyst, allowing surface H atoms to add to a second, perhaps physically adsorbed layer of ethylene this is, in effect, a kind of Eley-Rideal mechanism. 

A few industrial catalysts have simple compositions, but the typical catalyst is a complex composite made up of several components, illustrated schematically in Figure 9 by a catalyst for ethylene oxidation. Often it consists largely of a porous support or carrier, with the catalyticaHy active components dispersed on the support surface. For example, petroleum refining catalysts used for reforming of naphtha have about 1 wt% Pt and Re on the surface of a transition alumina such as y-Al203 that has a surface area of several hundred square meters per gram. The expensive metal is dispersed as minute particles or clusters so that a large fraction of the atoms are exposed at the surface and accessible to reactants (see Catalysts, supported). 

In practice, 1—10 mol % of catalyst are used most of the time. Regeneration of the catalyst is often possible if deemed necessary. Some authors have advocated systems in which the catalyst is bound to a polymer matrix (triphase-catalysis). Here separation and generation of the catalyst is easy, but swelling, mixing, and diffusion problems are not always easy to solve. Furthermore, triphase-catalyst decomposition is a serious problem unless the active groups are crowns or poly(ethylene glycol)s. Commercial anion exchange resins are not useful as PT catalysts in many cases. 

There are 12 producers of ethylene oxide ia the United States. Table 9 shows the plant locations, estimated capacities, and types of processes employed. The total U.S. production capacity for 1992 was ca 3.4 x 10 metric tons. The percentages of total domestic production made by the air- and oxygen-based processes are ca 20 and 80%, respectively. The largest producer is Union Carbide Corp. with approximately one-third of the United States ethylene oxide capacity. About 94% of domestic ethylene oxide capacity is located on the Gulf Coast near secure and plentiful ethylene suppHes. Plans for additional U.S. production ia the 1990s have been announced by Union Carbide (incremental expansions), Eormosa Plastics (at Pt. Comfort, Texas), and Shell (at Geismar, Louisiana) (101). 

A common property of coordinated alkenes is their susceptibility to attack by nucleophiles such as OH , OMe , MeC02, and Cl , and it has long been known that Zeise s salt is slowly attacked by non-acidic water to give MeCHO and Pt metal, while corresponding Pd complexes are even more reactive. This forms the basis of the Wacker process (developed by J. Smidt and his colleagues at Wacker Chemie, 1959-60) for converting ethene (ethylene) into ethanal (acetaldehyde) — see Panel overleaf. 

Another means of in situ metal-carbene complex formation in an ionic liquid is the direct oxidative addition of the imidazolium cation to a metal center in a low oxidation state (see Scheme 5.2-2, route b)). Cavell and co-workers have observed oxidative addition on heating 1,3-dimethylimidazolium tetrafluoroborate with Pt(PPli3)4 in refluxing THF [32]. The Pt-carbene complex formed can decompose by reductive elimination. Winterton et al. have also described the formation of a Pt-car-bene complex by oxidative addition of the [EMIM] cation to PtCl2 in a basic [EMIM]C1/A1C13 system (free CP ions present) under ethylene pressure [33]. The formation of a Pt-carbene complex by oxidative addition of the imidazolium cation is displayed in Scheme 5.2-4. 

Fig. 2. Pressure fall —AP (Torr) against time t (arbitrary units) in hydrogenation of acetylene on Pt/AhOa catalyst at 110°C and Pst/Pctnt 2. In the initial slow period of the reaction the main product is ethylene, and after the acceleration, further hydrogenation of ethylene to ethane predominates. From G. C. Bond and P. B. Wells, J. CaM. 4, 211 (1965).

S. Bebelis, and C.G. Vayenas, Non-Faradaic Electrochemical Modification of Catalytic Activity 1. The case of Ethylene Oxidation on Pt, J. Catal. 118, 125-146 (1989). 

The effect of alkali presence on the adsorption of oxygen on metal surfaces has been extensively studied in the literature, as alkali promoters are used in catalytic reactions of technological interest where oxygen participates either directly as a reactant (e.g. ethylene epoxidation on silver) or as an intermediate (e.g. NO+CO reaction in automotive exhaust catalytic converters). A large number of model studies has addressed the oxygen interaction with alkali modified single crystal surfaces of Ag, Cu, Pt, Pd, Ni, Ru, Fe, Mo, W and Au.6... 

The effect of the presence of alkali promoters on ethylene adsorption on single crystal metal surfaces has been studied in the case ofPt (111).74 77 The same effect has been also studied for C6H6 and C4H8 on K-covered Pt(l 11).78,79 As ethylene and other unsaturated hydrocarbon molecules show net n- or o-donor behavior it is expected that alkalis will inhibit their adsorption on metal surfaces. The requirement of two free neighboring Pt atoms for adsorption of ethylene in the di-o state is also expected to allow for geometric (steric) hindrance of ethylene adsorption at high alkali coverages. 

Figure 2.25. C2H4 (a), H2 (b) and C2H6 (c) TPD spectra recorded after ethylene adsorption on clean and K-covered Pt(l 11). Ta = 100 K. 0K values are relative to the saturation K coverage in the first layer taken as unity. Inset effect of 0k on C2H6 TPD area. The real coverage in monolayers (K adatoms per surface atom) is 3.03 times smaller.74 Reprinted with permission from Elsevier Science.

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