Reactivity of lanthanides

Hoppe D, Marr F, Bruggemann M (2003) Enantioselective Synthesis by Lithiation Adjacent to Oxygen and Electrophile Incorporation. 5 61-138 Hou Z, Wakatsuki Y (1999) Reactions of Ketones with Low-Valent Lanthanides Isolation and Reactivity of Lanthanide Ketyl and Ketone Dianion Complexes. 2 233-253 Hoveyda AH (1998) Catalytic Ring-Closing Metathesis and the Development of Enantioselective Processes. 1 105-132 Huang M, see Wu GG (2004) 6 1-36... 

Fig. 2 Reactivity of lanthanide phenolates toward trialkylaluminum reagents R3AI...

Scheme 42 Reactivity of lanthanide amide complexes with organoaluminum or borate reagents...

Scheme 45 Reactivity of lanthanide silylamide complexes toward trialkylaluminum R3AI (R = Me, Et, i-Bu CpR = substituted cyclopentadienyl ligand)...

Synthesis and Reactivity of Lanthanide Complexes Containing Ln-C o-Bonds... 

Voskoboynikov, A.Z., Parshina, I.N., Shestakova, A.K. et al. (1997) Reactivity of lanthanide and yttrium hydrides and hydrocarbyls toward organosilicon hydrides and related compounds. Organometallics, 16, 4041. 

Reactions of Ketones with Low-Valent Lanthanides Isolation and Reactivity of Lanthanide Ketyl and Ketone Dianion Complexes... 

The protonation reaction of the Yb(II) fluorenone dianion species with ArOH is similar to the major reaction of the Yb(II) benzophenone dianion 14 with ArOH, occurring at both the C and O atoms of the carbonyl unit to afford Id and fluore-nol (Scheme 20). However, the protonation reaction of the Sm(II) fluorenone dianion species with ArOH takes place only at the C atom and is accompanied by the oxidation of the Sm(II) ion to give the corresponding samarium(III) ary-loxide/fluorenoxide complex 20 (Scheme 20), which again demonstrates the metal dependence of the reactivity of lanthanide ketone dianion species [22]. 

That the reactivity of lanthanide active centres depends on the nature of AIR3 follows also from the microstructure of polydienes. Varying AIR3 component results in changes in the relative number of c/s-1,4 and trans-l,4-units in polybutadiene. At the same time, the content of 1,2-units remains the same (abont 0.6% at 25 °C). The only exception is a catalyst with diisobutylalnminnm hydride, in which case, approximately a three-fold increase in the content of 1,2-imits is observed. As the concentration of butadiene decreases (<0.5 /o mol/1) and the polymerisation temperatnre increases (from 25 to 80 the dependence of the number of cis-l,4-units in the polymer on the structure of AIR3 becomes more pronounced [10]. 

In parallel with the catalytic reactivity of early-transition-metal-alkoxo complexes, the catalytic reactivity of lanthanide-alkoxo and -phenoxo complexes has been developed. The homogenous hydrogenation of a variety of arene substrates can be catalyzed by niobium... 

Kudin, L.S., 2002. Complex Investigation of the Structure, Energy and Reactivity of Lanthanide Trichlorides by High Temperature Mass Spectrometry and Non Empirical Quantum Chemistry. RFBR Report 2002. Grant No. 01-03-32194 (in Russian). 

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