Yttrium hydride complex reaction with

The dissociation of the dimer [Cp 2Y(/i-H)]2 to the Cp 2YH monomer is an important process in the reactions of the dimer with alkenes. The kinetics and formation of yttrium alkyl complexes from [Cp 2Y(//-I I)]2 and alkenes have been investigated.587 In situ prepared dimeric bis(pentamethylcyclopentadienyl)yttrium hydride reacted rapidly with 3,3-dimethyl-l,4-pentadiene in methylcylohexane-r/ at — 78 °C and formed a bright yellow solution of the t/°-yttrium(m)pentenyl chelate complex Cp 2Y[7/,7/2-CI I2CI I2CMc2CI I=CH2] in 98% yield (Scheme 130). This pentenyl chelate complex was also prepared in toluene-// in 84% yield. The chelate complex was stable for about 2 weeks at — 78 °C but decomposed after a few hours at —50 °C. The complex was characterized without isolation by 1H and 13C NMR spectroscopy at —100 °C such complexes can be regarded as models for the coordination of alkenes to lanthanide and isoelectronic grouop 4 polymerization catalysts.588 Agostic interactions in yttrium alkyls of the type... 

Because lanthanide catalysts do not have the appropriate accessible oxidation states for reaction by a sequence of oxidative addition and reductiye elimination, an alternative mechanism is followed by these catalysts. These hydrosilylations are thought to occur by a version of a Qhalk-Harrod mechanism in which the C-Si bond is formed by u-bond metathesis instead of reductive elimination. As shown in Scheme 16.9, conversion of the alkyl precursor to a metal hydride is followed by insertion of the alkene to form a yttrium alkyl complex. Reaction of this alkyl complex with the silane generates the alkylsilane and the metal hydride in a u-bond metathesis process. 

Table 10 shows the results of polymerization of oc-olefins catalyzed with trivalent complexes. When a bulkiler tBuMe2Si group instead of the Me3Si group was introduced into the yttrium complex, the racemic complex was formed exclusively [74c]. However, this alkyl complex did not react with olefins, and hence it was converted to a hydride complex by reaction with H2. The complex obtained was reactive to various olefins and produced polymers at... 

The reaction of (C9H7)2LnCl(THF) with NaH in THF generates the dimeric bis(indenyl)lanthanide hydrides [(C9H7)2Ln(/r-H)]2 4THF-NaCl.695 The stereoselective synthesis and structural characterization of raf-planar chiral bis(2-methoxyethylindenyl)lanthanum and yttrium tetrahydroborate complexes has been achieved. The complexes... 

The dimeric yttrium and samarium hydride complexes are converted into monomers in the first step of the reaction. The preparation of block-co-polymers of 1-hexene or 1-pentene with MMA and e-caprolactone, respectively, has also been reported. The polymerization of ethylene with MMA, e-caprolactone and 2,2-dimethyltri-methylenecarbonate was studied in detail racemic Me2Si(CsH2-2-SiMe3-4-But)2Sm(THF)2 or meso-Me2Si(Me2SiOSiMe2)(CsH2-3-But)Sm(THF) were active in the ABA-type triblock-co-polymerization.986... 

A unique example of non metallocenic catalyst [(DADMB)YMe], [(DADMB) = 2,2 -bis(/er -butyldimethylsilylamido)-6,6 -dimethyldiphenyl], was recently reported [13]. It was assumed that the methyl complex first reacts with the silane to give a small concentration of a monomeric highly reactive hydride (Scheme 2). The yttrium hydride was not detected by NMR spectroscopy, probably because its concentration is very low. Nevertheless, precipitation of the insoluble yttrium dimer [(DADMB)YH]2 occurred at the end of the reaction. The bulky ligand... 

R CN (Table 2) [86]. The molecular structure of the 2,2-dimethylpropanonitrile derivative contains unsymmetrically bridging alkylidene amide ligands. Reaction of the yttrium and erbium hydride species with isonitrile results in the formation of a formidoyl moiety (Table 2) [87], Surprisingly the Ln-N interaction is in the range of the nitrile product A similar molecular structure was found in the oximato complex [Cp2Gd(/i-t/2-ONCMe2)]2 (Gd-Nav 2.42(1) A) [88]. 

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