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双三(吡唑基)硼酸镧系/铝异双金属三氢化物配合物的合成与反应性

Synthesis and Reactivity of Bis-tris(pyrazolyl)borate Lanthanide/Aluminum Heterobimetallic Trihydride Complexes.

作者信息

Chowdhury Tajrian, Murphy Fáinché, Kennedy Alan R, Wilson Claire, Farnaby Joy H, Weetman Catherine E

机构信息

Joseph Black Building, School of Chemistry, University of Glasgow, Glasgow G12 8QQ, U.K.

Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL, U.K.

出版信息

Inorg Chem. 2024 May 27;63(21):9390-9394. doi: 10.1021/acs.inorgchem.4c00824. Epub 2024 Apr 29.

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)(μ-H)Al(H)(N″)] [; Ln = Y, Sm, Dy, Yb; Tp = hydrotris(1-pyrazolyl)borate; N″ = N(SiMe)] have been synthesized by facile insertion of aminoalane [MeN·AlH] into the Ln-N amide bonds of [Ln(Tp)(N″)] (). Thus, this is a simple synthetic strategy to access a range of Ln/Al hydrides. Reactivity studies demonstrate that is a heterobimetallic hydride, with evidence for the cooperative nature of shown by the catalytic amine-borane dehydrocoupling under ambient conditions in contrast to its monomeric counterparts.

摘要

镧系(Ln)和主族(MG)金属的分子异双金属氢化物配合物展现出与其单金属对应物不同的独特化学性质,并且是高反应活性物种,这使得它们的合成和分离具有挑战性。在此,通过将氨基铝烷[MeN·AlH]轻松插入到[Ln(Tp)(N″)]()的Ln-N酰胺键中,合成了分子型Ln/Al异双金属三氢化物[Ln(Tp)(μ-H)Al(H)(N″)] [;Ln = Y、Sm、Dy、Yb;Tp = 氢化三(1-吡唑基)硼酸盐;N″ = N(SiMe)]。因此,这是一种获取一系列Ln/Al氢化物的简单合成策略。反应性研究表明,是一种异双金属氢化物,与单体对应物相比,在环境条件下催化胺-硼烷脱氢偶联显示出其协同性质的证据。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0ac1/11134492/9ffdf3f942e6/ic4c00824_0001.jpg

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