RESUMEN
Molecular heterobimetallic hydride complexes of lanthanide (Ln) and main-group (MG) metals exhibit chemical properties unique from their monometallic counterparts and are highly reactive species, making their synthesis and isolation challenging. Herein, molecular Ln/Al heterobimetallic trihydrides [Ln(Tp)2(µ-H)2Al(H)(Nâ³)] [2-Ln; Ln = Y, Sm, Dy, Yb; Tp = hydrotris(1-pyrazolyl)borate; Nâ³ = N(SiMe3)2] have been synthesized by facile insertion of aminoalane [Me3N·AlH3] into the Ln-N amide bonds of [Ln(Tp)2(Nâ³)] (1-Ln). Thus, this is a simple synthetic strategy to access a range of Ln/Al hydrides. Reactivity studies demonstrate that 2-Ln is a heterobimetallic hydride, with evidence for the cooperative nature of 2-Ln shown by the catalytic amine-borane dehydrocoupling under ambient conditions in contrast to its monomeric counterparts.
RESUMEN
On supercooling a liquid, the viscosity rises rapidly until at the glass transition it vitrifies into an amorphous solid accompanied by a steep drop in the heat capacity. Therefore, a pure homogeneous liquid is not expected to display more than one glass transition. Here we show that a family of single-component homogeneous molecular liquids, titanium tetraalkoxides, exhibit two calorimetric glass transitions of comparable magnitude, one of which is the conventional glass transition associated with dynamic arrest of the bulk liquid properties, while the other is associated with the freezing out of intramolecular degrees of freedom. Such intramolecular vitrification is likely to be found in molecules in which low-frequency terahertz intramolecular motion is coupled to the surrounding liquid. These results imply that intramolecular barrier-crossing processes, typically associated with chemical reactivity, do not necessarily follow the Arrhenius law but may freeze out at a finite temperature.
RESUMEN
Synthesis and reactivity with carbon dioxide (CO2) of divalent samarium in the bis-tris(pyrazolyl)borate ligand environment has been reported. In addition, CO2 activation and functionalisation by lanthanide silylamides in the bis-tris(pyrazolyl)borate ligand environment was demonstrated. Reduction of the Sm(III) precursor [Sm(Tp)2(OTf)] (Tp = hydrotris(1-pyrazolyl)borate; OTf = triflate) with KC8 yielded the insoluble Sm(II) multi-metallic coordination polymer [{Sm(Tp)2}n] 1-Sm. Addition of 1,2-dimethoxyethane (DME) to 1-Sm enabled isolation of the monomeric complex [Sm(Tp)2(DME)] 1-Sm(DME). Complex 1-Sm(DME) reduced CO2 to yield the oxalate-bridged dimeric Sm(III) complex [{Sm(Tp)2}2(µ-η2:η2-O2CCO2)] 2-Sm. The reactions of heteroleptic Ln(III) silylamide complexes [Ln(Tp)2(N'')] (Ln = Y, Sm; N'' = N(SiMe3)2) with CO2 yielded monomeric Ln(III) silyloxides [Ln(Tp)2(OSiMe3)] 3-Ln and trimethylsilyl isocyanate (OîCîNSiMe3). Complexes 3-Ln are the first crystallographically characterised examples of Ln(III)-OSiMe3 bonds accessed via CO2 activation and functionalisation. Full characterisation data are presented for all complexes, including solid-state molecular structure determination by single-crystal X-ray diffraction.
RESUMEN
Reduction of the heteroleptic Ln(III) precursors [Ln(Tp)2(OTf)] (Tp = hydrotris(1-pyrazolyl)borate; OTf = triflate) with either an aluminyl(I) anion or KC8 yielded the adduct-free homoleptic Ln(II) complexes dimeric 1-Eu [{Eu(Tp)(µ-κ1:η5-Tp)}2] and monomeric 1-Yb [Yb(Tp)2]. Complexes 1-Ln have good solubility and stability in both non-coordinating and coordinating solvents. Reaction of 1-Ln with 2 Ph3PO yielded 1-Ln(OPPh3)2. All complexes are intensely coloured and 1-Eu is photoluminescent. The electronic absorption data show the 4f-5d electronic transitions in Ln(II). Single-crystal X-ray diffraction data reveal first µ-κ1:η5-coordination mode of the unsubstituted Tp ligand to lanthanides in 1-Eu.