Factors affecting the reactivity of organolanthanide complexes
The factors affecting the reactivity of organolanthanide and organoyttrium complexes were probed by hydrogenolysis and thermal reactions. Hydrogenolysis of the complexes ((C/sub 5/H/sub 4/R)/sub 2/LnCH/sub 3/)/sub 2/ (R = H, CH/sub 3/; Ln = Er, Lu, Y, Yb), (C/sub 5/H/sub 4/R)>LnR' (R = H, CH/sub 3/; Ln = Lu, Y, Yb; R' = CH/sub 2/SiMe/sub 3/, CMe/sub 3/) and ((C/sub 5/H/sub 4/R)/sub 2/LnR'/sub 2/) (Li(S)/sub 4/) (R = H, CH/sub 3/; Ln = Y, Yb; R' = CH/sub 3/, CH/sub 2/SiMe/sub 3/, (S) = dimethoxyethane, tetramethylethylenediamine) revealed the importance of steric effects and solvation to the reactivity of biscyclopentadienyl alkyl and dialkyl complexes. Using these data, optimum conditions for obtaining ytterbium hydrides were determined, and the ytterbium hydride analogues of ((C/sub 5/H/sub 5/)/sub 2/YH(THF))/sub 2/ and /((C/sub 5/H/sub 4/)YH)/sub 3/H//Li(THF)/sub 4// were prepared. Thermolysis of the complexes (C/sub 5/H/sub 4/R)/sub 2/ Y(CH/sub 2/SiMe/sub 3/) (THF) and (C/sub 5/H/sub 5/)/sub 2/ YbCH/sub 3/ (THF) resulted in the formation of the enolate complexes ((C/sub 5/H/sub 4/R)/sub 2/Ln(..mu..-OCH = CH/sub 2/)/sub 2/. These complexes can also be generated by the metathesis reaction involved LiOHC = CH/sub 2/ and ((C/sub 5/H/sub 4/R)/sub 2/LnCl)/sub 2/. The effect of coordinating solvent upon the stability of organolanthanide complexes is also discussed. Application of the principles revealed by these investigated led to the successful synthesis of the monocyclopentadienyl complexes ((C/sub 5/H/sub 4/R)Y(CH/sub 2/SiMe/sub 3/)/sub 3/)(Li(S)/sub 4/) (R = H, CH/sub 3/' S/sub 4/ = (DME)/sub 2/, (THF)/sub 4/). Over the course of these investigations, the crystal structures of (C/sub 5/H/sub 5/)/sub 2/YbCH/sub 3/ (THF), ((CH/sub 3/C/sub 5/H/sub 4/)/sub 2/Y(..mu..-OCH = CH/sub 2/)/sub 2/, ((C/sub 5/H/sub 5/)/sub 2/Y(CH/sub 2/SiMe/sub 3/)/sub 2/)/sub 2/Li/sub 2/(CH/sub 3/OCH/sub 2/CH/sub 2/OCH/sub 3/)/sub 2/(..mu..-1,4-C/sub 4/H/sub 8/O/sub 2/) and ((C/sub 5/H/sub 5/)/sub 3/Y)/sub 2/(..mu..-1,4-C/sub 4/H/sub 8/O/sub 2/) were obtained.
- Research Organization:
- California Univ., Irvine (USA)
- OSTI ID:
- 6085140
- Resource Relation:
- Other Information: Thesis (Ph. D.)
- Country of Publication:
- United States
- Language:
- English
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SULFUR COMPOUNDS
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