Ethylene complexes with rhodium

In most cases the catalytically active metal complex moiety is attached to a polymer carrying tertiary phosphine units. Such phosphinated polymers can be prepared from well-known water soluble polymers such as poly(ethyleneimine), poly(acryhc acid) [90,91] or polyethers [92] (see also Chapter 2). The solubility of these catalysts is often pH-dependent [90,91,93] so they can be separated from the reaction mixture by proper manipulation of the pH. Some polymers, such as the poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymers, have inverse temperature dependent solubihty in water and retain this property after functionahzation with PPh2 and subsequent complexation with rhodium(I). The effect of temperature was demonstrated in the hydrogenation of aqueous allyl alcohol, which proceeded rapidly at 0 °C but stopped completely at 40 °C at which temperature the catalyst precipitated hydrogenation resumed by coohng the solution to 0 °C [92]. Such smart catalysts may have special value in regulating the rate of strongly exothermic catalytic reactions. 

The use of silver fluoroborate as a catalyst or reagent often depends on the precipitation of a silver haUde. Thus the silver ion abstracts a CU from a rhodium chloride complex, ((CgH )2As)2(CO)RhCl, yielding the cationic rhodium fluoroborate [30935-54-7] hydrogenation catalyst (99). The complexing tendency of olefins for AgBF has led to the development of chemisorption methods for ethylene separation (100,101). Copper(I) fluoroborate [14708-11-3] also forms complexes with olefins hydrocarbon separations are effected by similar means (102). 

Chalk and Elarrod (11a) compared the above ethylene Pt(II) complex with chloroplatinic acid for hydrosilation, and found that each gave essentially the same results in terms of rate, yields, and products. Plati-num(II) complexes and rhodium(I) complexes were very much alike in their behavior. No system was found in which a palladium olefin complex brought about hydrosilation. In most systems the palladium complex was very rapidly reduced to the metal. 

Detailed mechanistic studies with respect to the application of Speier s catalyst on the hydrosilylation of ethylene showed that the process proceeds according to the Chalk-Harrod mechanism and the rate-determining step is the isomerization of Pt(silyl)(alkyl) complex formed by the ethylene insertion into the Pt—H bond.613 In contrast to the platinum-catalyzed hydrosilylation, the complexes of the iron and cobalt triads (iron, ruthenium, osmium and cobalt, rhodium, iridium, respectively) catalyze dehydrogenative silylation competitively with hydrosilylation. Dehydrogenative silylation occurs via the formation of a complex with cr-alkyl and a-silylalkyl ligands ... 

Ethylene is commonly chosen to illustrate homogeneous hydrogenation with Wilkinson s catalyst, but the process is actually very slow with this aJkene. The explanation lies with the formation of a stable rhodium ethylene complex, which does not readily undergo reaction with H,. Ethylene competes effectively with the solvent for the vacant coordination site created when triphcnylphosphinc dissociates from Wilkinson s catalyst and thus serves as an inhibitor to hydrogenation. 

The process is very slow because of the formation of stable rhodium ethylene complex, which does not readily undergo reaction with H2. 

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). 

Bhirud VA, Ehresmann JO, Kletnieks PW, Haw JF, Gates BC (2006) Rhodium complex with ethylene ligands supported on highly dehydroxylated MgO Synthesis, characterization, and reactivity. Langmuir 22 490... 

Some insight into the mechanisms of the iodine-promoted carbonylation has been obtained by radioactive tracer techniques [17] and low-temperature NMR spectroscopy [18]. The mechanism involves the formation of HI, which in a series of reactions forms with rhodium a hydrido iodo complex which reacts with ethylene to give an ethyl complex. Carbonylation and reductive elimination yield propionic acid iodide. The acid itself is then obtained after hydrolysis. The rate of carboxylation was reported to be accelerated by the addition of minor amounts of iron, cobalt, or manganese iodide [19]. The rhodium catalyst can be stabilized by triphenyl phosphite [20]. However, it is doubtful whether the ligand itself would meet the requirements of an industrial-scale process. 

RhCl(C2H4)pip2] is formed as the actual catalyst. The complex, whose structure is established by X-ray crystal structure analysis [18], can be easily prepared by piperidine addition to the well-known [Rh(C2H4)2Cl]2, which shows identical catalytic properties. The catalytic efficiency is limited by the thermal instability of the bis(piperidine) ethylene complex at higher temperatures. The thermal decomposition proceeds with formation of metallic rhodium, presumably according to eq. (5). 

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