ABSTRACT
Following the alkane-elimination route, the reaction between tetravalent aryl tintrihydride Ar*SnH3 and trivalent rare-earth-metallocene alkyls [Cp*2 Ln(CH{SiMe3 }2 )] gave complexes [Cp*2 Ln(µ-H)2 SnAr*] implementing a low-valent tin hydride (Ln=Y, Lu; Ar*=2,6-Trip2 C6 H3 , Trip=2,4,6-triisopropylphenyl). The homologous complexes of germanium and lead, [Cp*2 Ln(µ-H)2 EAr*] (E = Ge, Pb), were accessed via addition of low-valent [(Ar*EH)2 ] to the rare-earth-metal hydrides [(Cp*2 LnH)2 ]. The lead compounds [Cp*2 Ln(µ-H)2 PbAr*] exhibit H/D exchange in reactions with deuterated solvents or dihydrogen.
ABSTRACT
Yttrocene derivatives [Cp*2Y(MMe4)] (Cp* = C5Me5; M = Al, Ga) and Cp*2Y[Me3Al{B(NDippCH)2}] (Dipp = C6H3iPr2-2,6) deprotonate benzene at elevated temperatures via the release of methane. The formation of [Cp*2Y(Me2MPh2)] (M = Al, Ga), Cp*2Y(MPh4) (M = Al, Ga), Cp*2Y[Me2AlPh{B(NDippCH)2}], and Cp*2Y[AlPh3{B(NDippCH)2}] can be controlled via the temperature applied. The activation temperature and formation of the coordinatively unsaturated "reactive" [Cp*2YMe] strongly depend on the coordination strength of the displaceable Lewis acids [AlMe3]2, GaMe3, and [Me2Al{B(NDippCH)2}]2. Hence, [Cp*2Y(AlMe4)] requires temperatures above 100 °C to metalate benzene, while Cp*2Y[AlMe3{B(NDippCH)2}] undergoes C-H-bond activation even at ambient temperatures. A kinetic deuterium isotope effect was observed for the reactions in C6D6 solutions. Distinct differences in the stabilities of the bulky Group 13 anions ([Me2MPh2]-, [MPh4]-, [Me3Al{B(NDippCH)2}]-, [Me2AlPh{B(NDippCH)2}]-, and [AlPh3{B(NDippCH)2}]-) are assessed by detailed studies of the coordination chemistry with tetrahydrofuran (THF) and by variable-temperature 1H NMR spectroscopy. Thus, increased steric bulk or a reduced Lewis acidity of the Group 13 metal center promote temperature-sensitive dissociation of trivalent Group 13 alkyl entities. Consequently, compound Cp*2Y[AlPh3{B(NDippCH)2}] was found to engage in a dissociation equilibrium with [Cp*2YPh] and AlPh2{B(NDippCH)2} in a C6D6 solution at ambient temperature. The reaction of Cp*2Y[AlPh3{B(NDippCH)2}] with THF results in the concomitant formation of monometallic Cp*2YPh(THF) and the solvent-separated ion pair [Cp*2Y(THF)2][AlPh3{B(NDippCH)2}].
ABSTRACT
Thermal treatment of Cp*2YMe(thf) (Cp* = C5Me5), obtained from Cp*2Y(AlMe4) via donor-induced AlMe3 cleavage, in THF resulted in the concomitant formation of vinyl oxide Cp*2Y(OC2H3)(thf) and 2-ethylene-tetrahydrofuranyl complex Cp*2Y(2-C2H4-OC4H7) via the release of methane. In stark contrast, dissolving Cp*2La(AlMe4) in THF/n-hexane led to the quantitative formation of AlMe3-stabilized 2-tetrahydrofuranyl complex Cp*2La(2-AlMe3-OC4H7), with methane elimination.
ABSTRACT
Despite the eminent importance of metal alkylidene species for organic synthesis and industrial catalytic processes, molecular homoleptic metal methylene compounds [M(CH2 )n ] as the simplest representatives, have remained elusive. Reports on this topic date back to 1955 when polymeric [Li2 (CH2 )]n and [Mg(CH2 )]n were accessed by pyrolysis of methyllithium and dimethylmagnesium, respectively. However, the insoluble salt-like composition of these compounds has impeded their application as valuable reagents. We report that rare-earth metallocene methyl complexes [(C5 Me5 )2 Ln{(µ-Me)2 GaMe2 }] (Ln=Lu, Y) trigger the formation of homoleptic gallium methylene [Ga8 (µ-CH2 )12 ] from trimethylgallium [GaMe3 ] (Me=methyl) via a cascade C-H bond activation involving the dodecametallic clusters [(C5 Me5 )6 Ln3 (µ3 -CH2 )6 Ga9 (µ-CH2 )9 ] as crucial intermediates. Such gallium methylene compounds feature a reversible [Ga8 (µ-CH2 )12 ]/[Ga6 (µ-CH2 )9 ] oligomer switch in donor solvents and act as Schrock-type methylene-transfer reagents.
