Organolanthanide hydride chemistry. 2. Synthesis and x-ray crystallographic characterization of a trimetallic organolanthanide polyhydride complex

A Double Addition of LnH to a Carbon–Carbon Triple Bond and Competitive Oxidation of Ytterbium(II) and Hydrido Centers

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The unique reactivity and catalytic activity of organolanthanide hydrido complexes in various transformations of unsaturated substrates has given a powerful incentive to development this chemistry. [1] Although rare-earth hydrides have been known since the 1980s, [2] until very recently they were represented exclusively by Ln III derivatives. The first structurally defined Ln II hydrido complex supported by bulky hydrotris(pyrazolyl)borate ligand was published by Takats et al in 1999.

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DIBAH‐Mediated Amide/Hydride Transformation in ansa‐Lanthanidocene(III) Complexes

“…[5] Such highly reactive discrete molecular hydride complexes are commonly synthesized, both on a preparative scale or in situ, by hydrogenolysis of lanthanidocene alkyl complexes. [6] Less cumbersome synthetic routes comprise: a) thermal decomposition [7] or silanolysis of alkyl derivatives, [8] b) salt metathesis of lanthanidocene(iii) chloride complexes with NaH or LiAlH 4 , [9,10] and c) oxidation of samarocene(ii) complexes with AlH 3 (NEt 3 ). [11] Recently, we applied an ™extended silylamide route∫ [12] to generate heteroleptic lanthanidocene(iii) bis(dimethylsilyl)amide complexes, including the first Brintzinger-type, indenyl-derived ansa-lanthanidocene derivatives.…”

“…[7] The availability of two m-iBu groups in lanthanidocene complexes was recently evidenced for [Cp * 2 Sm(m-iBu) 2 Ali-Bu 2 ] and rac-[{Me 2 Si(2-Me-C 9 H 5 ) 2 }Y(m-iBu) 2 AliBu 2 ]. [7] The availability of two m-iBu groups in lanthanidocene complexes was recently evidenced for [Cp * 2 Sm(m-iBu) 2 Ali-Bu 2 ] and rac-[{Me 2 Si(2-Me-C 9 H 5 ) 2 }Y(m-iBu) 2 AliBu 2 ].…”

Molecular Rare‐Earth‐Metal Hydrides in Non‐Cyclopentadienyl Environments

“…[1] Molecular rare-earth-metal hydrides were mostly limited to those supported by the bis(h 5 -cyclopentadienyl) or bent metallocene ligand frameworks. [1] Molecular rare-earth-metal hydrides were mostly limited to those supported by the bis(h 5 -cyclopentadienyl) or bent metallocene ligand frameworks.…”

“…The elegant use of cyclopentadienyl (Cp) ligands allowed the isolation and characterization of rare-earth-metal (Group 3 and the lanthanides) hydride complexes in the 1980s. [1] Molecular rare-earth-metal hydrides were mostly limited to those supported by the bis(h 5 -cyclopentadienyl) or bent metallocene ligand frameworks. [2] Such complexes have played an essential role in studying s-bond metathesis and developing homogeneous catalysts, for example, for a-olefin hydrogenation, hydroelementation, and polymerization.…”