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À propos de : Yttrium Hydrido Complexes that Contain a Less“Constrained Geometry” Ligand: Synthesis, Structure,and Efficient Hydrosilylation Catalysis        

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  • Yttrium Hydrido Complexes that Contain a Less“Constrained Geometry” Ligand: Synthesis, Structure,and Efficient Hydrosilylation Catalysis
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  • σ-Bond metathesis of the new linked amino-cyclopentadiene (C5Me4H)CH2SiMe2NHCMe3with Y(CH2SiMe3)3(THF)2 gave the alkyl-yttrium complex [Y(η5:η1-C5Me4CH2SiMe2NCMe3)(CH2SiMe3)(THF)] (1) in 66% yield. Compound 1 was characterized by NMR spectroscopyand X-ray crystal structure analysis. By hydrogenolysis, 1 was quantitatively converted intothe dimeric hydride [Y(η5:η1-C5Me4CH2SiMe2NCMe3)(THF)(μ-H)]2 (2). X-ray crystal structureanalysis revealed a Y2H2 core connected to two [Y(η5:η1-C5Me4CH2SiMe2NCMe3)(THF)]fragments in a skewed manner, with a relatively long yttrium−yttrium distance of 3.7085(8)Å. In solution, two diastereomers were observed by 1H NMR spectroscopy at −78 °C. Dimer2 was shown to efficiently catalyze the hydrosilylation of 1-decene with PhSiH3 to give theterminal silane nC10H21SiH2Ph exclusively. Although the product of addition of the yttrium-hydride complex 2 to styrene, [Y(η5:η1-C5Me4CH2SiMe2NCMe3){CH(CH3)Ph}(THF)] (3),contains a 1-phenethyl ligand derived from internal addition, hydrosilylation of styrene withPhSiH3 catalyzed by 2 gave both terminal- and internal-hydrosilylated products in a ratioof 1:1.4.
  • The alkyl complex [Y(η5:η1-C5Me4CH2SiMe2NCMe3)(CH2SiMe3)(THF)] (1) is quantitatively converted by hydrogenolysis into the dimeric hydride [Y(η5:η1-C5Me4CH2SiMe2NCMe3)(THF)(μ-H)]2 (2). The hydride is an efficient hydrosilylation catalyst converting 1-decene with PhSiH3 into the terminal silane nC10H21SiH2Ph. Although the product of addition of the yttrium-hydride complex 2 to styrene, [Y(η5:η1-C5Me4CH2SiMe2NCMe3){CH(CH3)Ph}(THF)] (3), contains a 1-phenethyl ligand derived from internal addition, hydrosilylation of styrene gave both terminal- and internal-hydrosilylated products in a ratio of 1:1.4.
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