Cobalt complex, unmodified hydroformylation

The hydroformylation of conjugated dienes with unmodified cobalt catalysts is slow, since the insertion reaction of the diene generates an tj3-cobalt complex by hydride addition at a terminal carbon (equation 10).5 The stable -cobalt complex does not undergo facile CO insertion. Low yields of a mixture of n- and iso-valeraldehyde are obtained. The use of phosphine-modified rhodium catalysts gives a complex mixture of Cs monoaldehydes (58%) and C6 dialdehydes (42%). A mixture of mono- and di-aldehydes are also obtained from 1,3- and 1,4-cyclohexadienes with a modified rhodium catalyst (equation ll).29 The 3-cyclohexenecarbaldehyde, an intermediate in the hydrocarbonylation of both 1,3- and 1,4-cyclo-hexadiene, is converted in 73% yield, to the same mixture of dialdehydes (cis.trans = 35 65) as is produced from either diene. 

One of the earliest indications that the heterobimetallic [iW]cBER+UNi catalytic mechanism may exist came from the work on the addition of lanthanide complexes to unmodified cobalt-catalysed alkene hydroformylation [73]. Upon addition of the lanthanide complexes, a dramatic rate increase was observed. Lanthanides are known to readily generate highly reactive hydrides, and this would support the supposition that lanthanide hydrides are attacking the acyl cobalt complex RCOCo (CO)3/RCOCo(CO)4. In situ spectroscopic analysis was not available/reported. 

Modeling the Formate Ester Formation. Formate esters up to 4% of the total products are side products mainly in the unmodified cobalt-catalyzed alkene hydroformylation. Their formation has been explained in analogy to the Heck and Breslow mechanism of olefin hydroformylation (203). By the addition of HCo(CO)4 to the aldehyde carbonyl group, either an a-hydroxyaUgrl- or an alkoxy-cobalt carbonyl is formed. The latter complex converts with carbon monoxide into an (alkoxycarbonyl)cobalt carbonyl. Reduction of this complex gives the formate product (Scheme 15). 

Bearing in mind the greater atomic radius of Rh, it becomes apparent why an unmodified rhodium catalyst generates a greater amount of branched aldehydes in comparison to the cobalt congener. For example, in the hydroformylation of 1-pentene, an Hb ratio of only 1.6 1 was found, while with the cobalt complex a ratio of 4 1 resulted. A similar correlation has been qualitatively deduced from reactions mediated by the metal clusters Rug(CO)j 2> 0 3(00)22, and 4(00)22. Because of the larger atomic radii of the metals, in hydroformylation these catalysts produce more branched aldehydes than observed in the reaction with Co2(CO)g. Unfortunately, most of these results were achieved under different reaction conditions or are difficult to interpret because of low reaction rates and are therefore not strictly comparable. 

Typical examples of different behavior in relation to the metal are trivalent phosphorus ligands. Thus, trials to modify cobalt complexes with PPhg proved rather problematic, due to the shift of the equilibrium to the left-hand side, especially under increased CO pressure (Scheme 1.7). As a consequence, the hydroformylation is catalyzed by the unmodified Co complex. Diphosphines of the type Ph2PZPPh2 (Z = (CH2)2, (CH2)4, CH=CH) cause a dramatic decrease in reactivity [19]. Also, phosphites do not form active hydroformylation catalysts with cobalt. It seems that only basic trialkyl phosphines are suitable for the generation of stable Co phosphine hydroformylation catalysts. 

Cobalt carbonyls are the oldest catalysts for hydroformylation and they have been used in industry for many years. They are used either as unmodified carbonyls, or modified with alkylphosphines (Shell process). For propene hydroformylation, they have been replaced by rhodium (Union Carbide, Mitsubishi, Ruhrchemie-Rhone Poulenc). For higher alkenes, cobalt is still the catalyst of choice. Internal alkenes can be used as the substrate as cobalt has a propensity for causing isomerization under a pressure of CO and high preference for the formation of linear aldehydes. Recently a new process was introduced for the hydroformylation of ethene oxide using a cobalt catalyst modified with a diphosphine. In the following we will focus on relevant complexes that have been identified and recently reported reactions of interest. 

Of the isomeric aldehydes indicated in Eq. (7.1), the linear aldehyde corresponding to anti-Markovnikov addition is always the main product. The isomeric branched aldehyde may arise from an alternative alkene insertion step to produce the [RCH(Me)Co(CO)3] or [RCH(Me)Rh(CO)(PPh3)2] complexes, which are isomeric to 2 and 8, respectively. Alternatively, hydroformylation of isomerized internal alkenes also give branched aldehydes. The ratio of the linear and branched aldehydes, called linearity, may be affected by reaction conditions, and it strongly depends on the catalyst used. Unmodified cobalt and rhodium carbonyls yield about 3-5 1 mixtures of the normal and iso products. 

In the early 1960s Heck and Breslow formulated the generally accepted hydroformylation cycle depicted in Scheme 3 [89]. Originally formulated for cobalt catalysts, the mechanism is valid for unmodified rhodium complexes as well. The elemental steps (Scheme 3) are ... 

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