Rhodium-catalysed reactions carbene complexes

The rhodium-catalysed reaction between 1,3-azoles and terminal alkenes is thought to proceed via a carbene complex. ... 

The ligand was then used to form a variety of transition metal carbene complexes [207] (see Figure 3.72). Interestingly, more than one method for the formation of transition metal carbene complexes was successfully employed presence of an inorganic base (IC COj) to deprotonate the imidazolium salt and the silver(I) oxide method with subsequent carbene transfer to rhodium(I), iridium(I) and copperfi), respectively. The silver(I) and copper(I) carbene complexes were used for the cyclopropanation of styrene and indene with 1,1-ethanediol diacetate (EDA) giving very poor conversion with silver (< 5%) and qnantitative yields with copper. The diastereomeric ratio (endolexo) was more favonrable with silver than with copper giving almost a pnre diastereomer for the silver catalysed reaction of indene. 

Non-metathetical reactions catalysed by ruthenium-carbene complexes are multifaceted and cover a broad range of transformations, thanks in part to the large number of oxidation states and coordination geometries available for the metal centre, in sharp contrast with other elements such as rhodium, palladium and platinum, which reluctantly form compounds with high oxidation states and have a strong preference for the square planar geometry. Several... 

Figure 6.26. Carbene reaction catalysed by rhodium(II) complexes containing fluorinated...

An important factor in the efficiency of this reaction may well be complexation between the rhodium carbene and the bond into which carbene insertion is to take place certainly rhodium mediated C—H bond activation is known to take place. The addition to alkenes can also be catalysed " rearrangement of the product provides a useful route to cyclopentane rings. 

Reviews.—Recent reviews involving olefin chemistry include olefin reactions catalysed by transition-metal compounds, transition-metal complexes of olefins and acetylenes, transition-metal-catalysed homogeneous olefin disproportionation, rhodium(i)-catalysed isomerization of linear butenes, catalytic olefin disproportionation, the syn and anti steric course in bi-molecular olefin-forming eliminations, isotope-elfect studies of elimination reactions, chloro-olefinannelation, Friedel-Crafts acylation of alkenes, diene synthesis by boronate fragmentation, reaction of electron-rich olefins with proton-active compounds, stereoselectivity of carbene intermediates in cycloaddition to olefins, hydrocarbon separations using silver(i) systems, oxidation of olefins with mercuric salts, olefin oxidation and related reactions with Group VIII noble-metal compounds, epoxidation of olefins... 

Within the last few years there has been a growing tendency to draw the analogy between the chemistry of organometallic complexes and that of hydrocarbons adsorbed on metal atoms in surfaces. For example, it is postulated that the isotopic exchan between deuterium and alkanes, catalysed by thin films of nickel, palladium or rhodium, occurs via an equilibrium between a- and 7r-bonded metal-organic species [109, 110, 111, 112]. i-Bonded olefins are postulated in Zie er catalysis, see above, in the catalytic deuteration of aromatic complexes [113], and in a variety of isomerization reactions [112, 114, US]. Other intermediate metal-carbon systems which have been proposed in heterogeneous catalytic systems include carbenes , e.g. M= H2 [109], Ji-enyl systems [114] and of course the metal-carbonyl M—CO and bridging carbonyl M- O—M. 

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