Rare-earth-metal half-sandwich complexes incorporating methyl, methylidene, and hydrido ligands

Abstract

Complexes Cp*₃Ln₃(μ₂-CH₃)₃(μ₃-CH₂)(μ₃-H)(thf)₃ (Ln = Y, Dy; Cp* = C₅Me₅) are formed via elimination of CH₄ and C₂H₄ from the respective trinuclear polymethyl complexes [Cp*Ln(μ₂-CH₃)₂]₃, involving the methyl/methylidene complex Cp*₃Ln₃(μ₂-CH₃)₃(μ₃-CH₂)(μ₃-CH₃)(thf)₂ as an intermediate. Compound Cp*₃Y₃(μ₂-CH₃)₃(μ₃-CH₂)(μ₃-H)(thf)₃ displays “Schrock-type” nucleophilic carbene reactivity, converting ketones into the corresponding terminal alkenes. Treatment of Cp*₃Y₃(μ₂-CH₃)₃(μ₃-CH₂)(μ₃-H)(thf)₃ with [D₄]methanol proved accessibility of all small-group functionalities as indicated by the simultaneous formation of deuterated HD and deuterated methanes CH₃D and CH₂D₂.