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

Complexes Cp*(3)Ln(3)(mu(2)-CH3)(3)(mu(3)-CH2)(mu(3)-H)(thf)(3) (Ln = Y, Dy; Cp* = C5Me5) are formed via elimination of CH4 and C2H4 from the respective trinuclear polymethyl complexes [Cp*Ln(mu(2)-CH3)(2)](3), involving the methyl/methylidene complex Cp*(3)Ln(3)(mu(2)-CH3)(3)(mu(3)-CH2)(mu(3)-CH3)(thf)(2) as an intermediate. Compound Cp*Y-3(3)(mu(2)-CH3)(3)(mu(3)-CH2)(mu(3)-H)(thf)(3) displays Schrock-type nucleophilic carbene reactivity, converting ketones into the corresponding terminal alkenes. Treatment of Cp*Y-3(3)(mu(2)-CH3)(3)(mu(3)-CH2)(mu(3)-H)(thf)(3) with [D-4]methanol proved accessibility of all small-group functionalities as indicated by the simultaneous formation of deuterated HD and deuterated methanes CH3D and CH2D2.

Automated summary

New Cp*(3)Ln(3)(mu(2)-CH3)(3)(mu(3)-CH2)(mu(3)-H)(thf)(3) complexes are formed through the elimination of methane and ethylene, and they exhibit nucleophilic carbene reactivity. Various small-group functionalities can be accessed by treating these complexes.