Reactivity of halfsandwich rare-earth metal methylaluminates toward potassium (2,4,6-tri-tert-butylphenyl)amide and 1-adamantylamine

Abstract

Donor functionalities drastically affect salt-metathetical methylaluminato–amido exchange reactions in CpRLn(AlMe4)2 by triggering methylaluminate cleavage and C–H bond activation of proximal aliphatic groups.

Yttrium Siloxide Complexes Bearing Terminal Methyl Ligands: Molecular Models for Ln−CH3 Terminated Silica Surfaces

“…Before discussing the solid‐state structures of complexes 3 – 5 , a brief survey on known yttrium complexes bearing terminal methyl ligands is given . The most prominent examples are certainly [(C 5 Me 5 ) 2 Y(CH 3 )(THF)] (Y‐C(CH 3 ) terminal 2.44(2) Å) and dimeric unsolvated [(C 5 Me 5 ) 2 Y(CH 3 )(μ‐CH 3 )Y(C 5 Me 5 ) 2 ], the latter of which engages in methane activation .…”

“…[29][30][31][32][33][34][35][36][37][38] Them ostp rominent examples are certainly[(C 5 Me 5 ) 2 Y(CH 3 )(THF)]( Y-C(CH 3 ) terminal 2.44(2)) [29] andd imericu nsolvated[ (C 5 Me 5 ) 2 Y(CH 3 )(m-CH 3 )Y(C 5 Me 5 ) 2 ], thel attero f whichengages in methaneactivation. X-ray crystallographic studies Before discussing thes olid-state structures of complexes 3-5, ab rief survey on knowny ttrium complexesb earing terminal methyl ligandsi sg iven.…”

“…[37] Thesecomplexes were obtained by treatment of thecorresponding half-sandwichb is(tetramethylaluminate) complexes with [K{NH(mes*)}]a nd H 2 NAd, respectively.M oreover, as eries of donor-stabilized cationic complexeso ft he type [Y(CH 3 ) 2 (donor) x ] + and[ Y(CH 3 )(donor) y ] 2 + hasb eenr eported with YÀC(CH 3 ) terminal bond lengthsi nt he rangeo f2 .374(3)-2.526 (2) . [37] Thesecomplexes were obtained by treatment of thecorresponding half-sandwichb is(tetramethylaluminate) complexes with [K{NH(mes*)}]a nd H 2 NAd, respectively.M oreover, as eries of donor-stabilized cationic complexeso ft he type [Y(CH 3 ) 2 (donor) x ] + and[ Y(CH 3 )(donor) y ] 2 + hasb eenr eported with YÀC(CH 3 ) terminal bond lengthsi nt he rangeo f2 .374(3)-2.526 (2) .…”

“…Before discussing thes olid-state structures of complexes 3-5, ab rief survey on knowny ttrium complexesb earing terminal methyl ligandsi sg iven. [29][30][31][32][33][34][35][36][37][38] Them ostp rominent examples are certainly[(C 5 Me 5 ) 2 Y(CH 3 )(THF)]( Y-C(CH 3 ) terminal 2.44(2)) [29]…”

“…[30,31] Ad = adamantyl; 2.392(2) ) feature4 -membered Y-CH 3 -Al-N(amido) metallacycles. [37] Thesecomplexes were obtained by treatment of thecorresponding half-sandwichb is(tetramethylaluminate) complexes with [K{NH(mes*)}]a nd H 2 NAd, respectively.M oreover, as eries of donor-stabilized cationic complexeso ft he type [Y(CH 3 ) 2 (donor) x ] + and[ Y(CH 3 )(donor) y ] 2 + hasb eenr eported with YÀC(CH 3 ) terminal bond lengthsi nt he rangeo f2 .374(3)-2.526 (2) . [38] [K(AlMe 2 ){OSi(OtBu) 3…”