Sc and Y Heteroalkyl and Alkyl-Hydrido Complexes Containing Diphenylmethanide Ligands [2,2′-(4-MeC6H3NMe2)2CH]−

A series of Sc(III) and Y(III) heteroalkyl complexes were synthesized by salt metathesis reactions of chloro-bis(diphenylmethanides) {[2,2′-(4-MeC6H3NMe2)2CH]2Ln(μ-Cl)}2 (Ln = Sc, Y) and related alkali metal alkyl reagents (MeLi, Me3SiCH2Li, tBuLi, PhCH2K). The molecular structures of scandium [2,2′-(4-MeC6H3NMe2)2CH]2ScR (R = Me (3), CH2SiMe3 (4), tBu (5)) and yttrium [2,2′-(4-MeC6H3NMe2)2CH]2YCH2Ph(THF) (6) complexes were established by single crystal X-ray analysis, which revealed that diphenylmethanido ligands are κ2-C,N coordinated to Sc3+ and Y3+ ions. It was demonstrated that different Ln–C (diphenylmethanide vs alkyl or benzyl) bonds have different reactivity toward PhSiH3. The σ-bond metathesis reactions of 4 and 6 with PhSiH3 involve exclusively Ln–CAlkyl/Benzyl bonds and lead to the formation of dimeric hydrido-bis(diphenylmethanides) {[2,2′-(4-MeC6H3NMe2)2CH]2Ln(μ-H)}2 (Ln = Sc (7), Y (8)), while the Ln–CAr2 bonds remain untouched.