Synthesis and reactivity of bis-tris(pyrazolyl)borate lanthanide-aluminium heterobimetallic trihydride complexes

Chowdhury, Tajrian and Murphy, Fáinché and Kennedy, Alan R. and Wilson, Claire and Farnaby, Joy H. and Weetman, Catherine E. (2024) Synthesis and reactivity of bis-tris(pyrazolyl)borate lanthanide-aluminium heterobimetallic trihydride complexes. Inorganic Chemistry, 63 (21). pp. 9390-9394. ISSN 0020-1669 (https://doi.org/10.1021/acs.inorgchem.4c00824)

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Abstract

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)(N″)] [2-Ln; Ln = Y, Sm, Dy, Yb; Tp = hydrotris(1-pyrazolyl)borate; N″ = N(SiMe 3) 2] have been synthesized by facile insertion of aminoalane [Me 3N·AlH 3] into the Ln-N amide bonds of [Ln(Tp) 2(N″)] (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.