Organolanthanide-catalyzed Hydrogenation Reactions

Selective hydrogenation of conjugated diolefin polymers, especially co-polymers with alkenylaromatic hydrocarbons, has been achieved by treatment of the polymers with hydrogen in the presence of a catalyst comprising Cp 2LnR (R = H, alkyl, aryl) and an alkali metal promoter.881 

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The most thoroughly investigated group of organolanthanide-catalyzed reactions are monoolefin transformations. These include the following processes a) hydrogenation, b) oligomerization, c) polymerization, d) hydroamination, e) hydrosilylation, and f) hydroboration, which will be discussed in the above order. 

W.J.Evans (33,34) prepared some divalent organolanthanides by co-condensation at low temperature of lanthanide metal vapours with unsaturated hydrocarbons (cyclopentadienes, alkynes) containing acidic hydrogen. Some organolanthanides showed catalytic activity. Thus, Sm(C Me ) (THF) catalyzes hydrogenation of 3-hexyne into cis-hexene (cis trans > 99 1 under mild conditions 25°C, 1 atm of hydrogen. The reaction is believed to involve the addition of a hydride Ln-H to the triple bond followed by hydrogenolysis with H (35). The same complex polymerizes ethylene (35). /... 

Complexes of the 4 type catalyze the hydroboration of various olefins with catecholborane at ambient temperature [173], The proposed mechanism of the hydroboration reaction - although not within the scope of this book - parallels that of the hydrogenation and hydrosilylation reactions. The architecture of both olefins (terminal > terminal disubstituted > internal disubstituted > trisubstituted) and organolanthanides (TOF(La) 10 TOF(Sm) TOF(5) = 4 TOF(4) affects the rate of hydroboration, which for 4(La CH(SiMc3)2) and 1-hexene is TOF = 200 h , for example. The observed high regioselectivities are exclusively anti-Markovnikov. For smaller metal centers (Y, Zr, Ti) and other ligand systems (bis(cyclopentadienyl), bis(benzamidinato)) inactivation of the catalyst by catecholborane or Lewis base-metal complex induced disproportionation of catecholborane appeared to compete effectively with the catalytic conversion [174]. 

Chiral Cyclopentadienyl Complexes. Since the discovery of the polymerization activity of cyclopentadienyl complexes, they also play a key role in asymmetric catalysis (Fig. 13). Titanocene complexes of chiral tricyclic monocy-clopentadienyl ligand catalyze the enantioselective hydrogenation of unfunctionalized oleflns (105). A similar reaction has been performed with related catalysts such as chiral Ziegler-Natta systems (106) and organolanthanide systems (107). 

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