Rhodium iodide complex

In SILP carbonylation we have introduced a new methanol carbonylation SILP Monsanto catalyst, which is different from present catalytic alcohol carbonylation technologies, by using an ionic liquid as reaction medium and by offering an efficient use of the dispersed ionic liquid-based rhodium-iodide complex catalyst phase. In perspective the introduced fixed-bed SILP carbonylation process design requires a smaller reactor size than existing technology in order to obtain the same productivity, which makes the SILP carbonylation concept potentially interesting for technical applications. 

The halide exchange protocol also allows the use of other nucleophiles such as activated methylenes. The rhodium iodide complex was found to be the most... 

In 1968 Monsanto reported a chemically related process based on rhodium iodide complexes. Due to its high reaction rates, high selectivity and different kinetics, the process differs substantially from the cobalt process. Commercialization was achieved in 1970. Operating conditions are remarkably mild 30 bar, 180°C. 

The mechanism of the cobalt- (BASF), rhodium- (Monsanto), and iridium- (Cativa) catalyzed reaction is similar but the rate-determining steps differ and different intermediate catalyst complexes are involved. In all three processes two catalytic cycles occur. One cycle involves the metal carbonyl catalyst (II) and the other the iodide promoter (i). For a better overview only the catalytic cycle of the rhodium-catalyzed Monsanto process is presented in detail (Figure 6.15.4). Initially the rhodium iodide complex is activated with carbon monoxide by forming the catalytic active [Rhi2(CO)2] complex 4. Further the four-coordinated 16-electron complex 4 reacts in the rate-determining step with methyl iodide by oxidative addition to form the six-coordinated 18-electron transition methyl rhodium (I II)... 

As shown in Scheme 168, oxidative addition reactions with either methyl chloride or methyl iodide proved successful and yielded the corresponding octahedral rhodium(III) complexes. ... 

Several rhodium(I) complexes have also been employed as ATRP catalysts, including Wilkinson s catalyst, (177),391 421 422 ancj complex (178).423 However, polymerizations with both compounds are not as well-controlled as the examples discussed above. In conjunction with an alkyl iodide initiator, the rhenium(V) complex (179) has been used to polymerize styrene in a living manner (Mw/Mn< 1.2).389 At 100 °C this catalyst is significantly faster than (160), and remains active even at 30 °C. A rhenium(I) catalyst has also been reported (180) which polymerizes MM A and styrene at 50 °C in 1,2-dichloroethane.424... 

An anionic rhodium iodide carbonyl complex was supported on polyvinylpyrrolidone for the carbonylation of methanol in the presence of scC02 [98], Depending on the reaction conditions and method of extraction, less than 0.08% rhodium leaching was observed. Saturation of the support with methyl iodide was found to be vital to enhance the longevity and recyclability of the catalyst. 

We would have thought the same thing after some studies of the competition between chloride, bromide, and iodide for some rhodium(III) complexes, because we found that the ratios of the rate constants at 50°C. were very nearly 1 1 1. However, when activation energies were measured, we found that these produce a much bigger discrimination. In fact, the activation energy for the addition of iodide to our reactive intermediates is no less than 6 kcal. greater than the activation energy for addition of chloride and bromide. 

Ethanol421 is carbonylated to propionic acid, and isopropanol422 is carbonylated to n- and iso-butyric acids. In the latter case it is not known whether the isomerization occurs in the alcohol, the iodide or the rhodium-alkyl complex. 

Reactions of rhodium porphyrins with diazo esters - According to Callot et al., iodorhodium(III) porphyrins are efficient catalysts for the cyclopropanation of alkenes by diazo esters [320,321], The transfer of ethoxycarbonylcarbene to a variety of olefins was found to proceed with a large syn-selectivity as compared with other catalysts. In their study to further develop this reaction to a shape-selective and asymmetric process [322], Kodadek et al. [323] have delineated the reaction sequences (29, 30) and identified as the active catalyst the iodoalkyl-rhodium(III) complex resulting from attack of a metal carbene moiety Rh(CHCOOEt) by iodide. 

Step (1) involves the formation of methyl iodide, which then reacts with the rhodium complex Rh(I)L by oxidative addition in a rate-determining step (2) to form a methylrhodium(III) complex. Carbon monoxide is incorporated into the coordination sphere in step (3) and via an insertion reaction a rhodium acyl complex is formed in step (4). The final step involves hydrolysis of the acyl complex to form acetic acid and regeneration of the original rhodium complex Rh(I)L and HI. Typical rhodium compounds which are active precursors for this reaction include RhCl3, Rh203, RhCl(CO)(PPh3)2, and Rh(CO)2Cl2. 

Anionic metal complexes, for example [Rh(CO)2l2], can be exchanged onto the anion-exchange resin Dowex 1-X8. The supported rhodium carbonyl iodide complex functions as an immobilized methanol Carbonylation catalyst. Metal complexes of the water-soluble phosphine TPPTS and its monosulfonated analog have also been exchanged onto anion-exchange resins. The pendant sulfonate groups provide the electrostatic attraction to the support. 

Prior to these investigations by HCC the promotional effect of iodide on the oxidative addition of Mel was investigated by others [9, 39, 40]. Foster demonstrated that the rate enhancement of this reaction in anhydrous medium was attributable to increased nucleophilicity of the rhodium catalyst with added iodide. The rationale for this observation was the generation of an anionic rhodium carbonyl complex, [Rh(CO)2l(L)]. Generation of this species was observed only with iodide added to certain neutral Rh species. No rate enhancement occurred with iodide added to the anionic complex, [Rh(CO)2l2] [39]. Similarly, in solvents with a high water concentration, iodide salts exhibited no rate enhancement in the presence of [Rh(CO)2l2] [11]. Maitlis and co-workers, in more recent investigations, reported a promotional effect of iodide in aprotic solvents on the oxidative addition of CH3I on [Rh(CO)2l2] [9a, 9c]. 

A complementary, but less pronounced, increase in cis syri) selectivity is provided when diazoacetates with rather small ester groups and rhodium catalysts with bulky ligands, such as iodorhodium(IIl) porphyrins and mcso-tetrakis(2,4,6-triarylbenzoato)di-rhodium(ll) complexes, are employed. For ethyl 2-alkylcyclopropane-l-carboxylates so obtained, a cisfran.s ratio of 2-4 was typical. Notable cis selectivities have also been achieved in the synthesis of ethyl 2-phenylcyclopropane-l-carboxylate with the catalyst [(r/ -C5H5)Fe(CO)2(THF)][BFJ (cis/trans 5.25, see Section 1.2.1.2.4.2.6.3.1.) and copper catalysts prepared in situ from a copper salt [copper(I) iodide, copper(II) acetate or triflate] and sodium tetrakis(7,8,8-trimethyl-4,5,6,7-tetrahydro-2Ff-4,7-methanoindazolyl)borate (3) cis/ trans 2.1-3.2). °... 

A considerable increase in sensitivity is obtained when bromide [41] or iodide [42] is used instead of chloride. In the bromide method, a yellow-orange complex is obtained (e = 2.9-10" at max 427 nm a = 0.29). The rhodium-tin(II) iodide complex is red and has an absorption maximum at 460 nm (e = 3.9-10 a = 0.34). In the iodide method, the optimum concentration of HCl is 1 M. The concentration of KI should not be lower than 4% in the final coloured solution. The quantity of SnCF only slightly affects the absorbance. The iodine liberated by air in the initial stage of the procedure is reduced when the SnCh is added. 

An alternative to sequential reductive elimination and hydrolysis of acetyl iodide is direct reaction of water with a rhodium acetyl complex to give acetic acid. The relative importance of these two alternative pathways has not yet been fully determined, although the catalytic mechanism is normally depicted as proceeding via reductive elimination of acetyl iodide from the rhodium center. 

The efficacy of an iridium/iodide catalyst for methanol carbonylation was discovered by Monsanto at the same time as their development of the process using the rhodium/iodide catalyst [5]. Mechanistic investigations by Forster employing in situ HPIR spectroscopy revealed additional complexity compared to the rhodium system [115]. In particular, the carbonylation rate and catalyst speciation were found to show a more complicated dependence on process variables, and three distinct regimes of catalyst behavior were identified. At relatively low concentrations of Mel, H20, and ionic iodide, a neutral iridium (I) complex [Ir(CO)sI] was found to dominate, and the catalytic reaction was inhibited by increasing the CO partial pressure. Addition of small amounts of a quaternary ammonium iodide salt caused the dominant iridium species to become an Ir(III) methyl complex, [Ir(CO)2l3Me]. Under these conditions, the rate... 

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