Iron complexes bimetallic systems

The transfer of a nitrene from PhI=NTos as a commercial source can also be catalyzed by a bimetallic iron complex which exhibits moderate activity, as reported by Avenier and Latour (Scheme 9.12) [24]. The iron complex 10 is better suited for aliphatic substrates where better yields were reported compared with copper catalyst systems applied to the same reactions. 

The bridging phosphide group in bimetallic transition metal complexes appeared to participate in a transformation, rather than behave as an inert spectator ligand. This is particularly obvious in homobimetallic iron and cobalt systems.Mays et al. showed that the reactions of iron-cobalt phosphido-bridged complex 25 with both symmetrical and unsymmetrical alkynes gave five-membered ferracycle-containing compounds, such as 26, in which a CO and an alkyne were inserted regiospecifically into a Co-P bond in 25. Subsequent decarbonylation led to a set of four-membered ferracyclic species 27-30 in low yields. 

Fe—Fe bond can be assigned structures 201 or 202 based on spectral data. The other product of this reaction is 193 (R = r-Bu), however, it is produced in minor amounts. Complexes 199 (R = R = r-Bu, R = Ph, R = r-Bu) were obtained. Reaction of 146 (M = Mo, R = Ph, R = R = Ft, R = r" = Me) with (benzyli-deneacetone)iron carbonyl gives rise to the bimetallic complex 200 (M = Mo), which reacts further with the free phosphole to form the bimetallic heteronuclear sandwich 203. The preferable coordination of the molybdenum atom to the dienic system of the second phosphole nucleus is rather unusual. The molybdenum atom is believed to have a greater tendency to coordinate via the trivalent phosphorus atom than via the dienic system. 

As mentioned above, the addition of promoters, and even the formation of bimetallic particles, can provide carbon-supported iron catalysts with better performances in CO hydrogenation. The method of preparation of these systems is going to determine the final effect, always taking advantage of the relative inertness of the carbon surface. The interaction between the different components of the active phase can be maximized by using mixed-metal carbonyl complexes. Furthermore, use of these precursors allows for the preparation of catalysts with... 

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