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异双金属镱-铂-烷基配合物的制备及基态电子结构

Preparation and Ground-State Electronic Structure of Heterobimetallic Yb-Pt-Alkyl Complexes.

作者信息

Tricoire Maxime, Danoun Grégory, Nocton Grégory

机构信息

LCM, CNRS, École Polytechnique, Institut Polytechnique de Paris, Route de Saclay, Palaiseau 91120, France.

出版信息

Inorg Chem. 2024 Oct 21;63(42):19728-19737. doi: 10.1021/acs.inorgchem.4c02921. Epub 2024 Oct 10.

DOI:10.1021/acs.inorgchem.4c02921
PMID:39387267
Abstract

This article focuses on the synthesis of heterobimetallic complexes of lanthanide and platinum. It describes the synthesis of the Cp*Yb(bipym)PtMe complex and its characterization, followed by its reactivity with oxidants, giving access to various Pt + IV compounds of trismethyl (PtMe) and tetramethyl (PtMe) fragments. Characterization of the electronic properties of the complexes by magnetic measurements demonstrated that the tetramethyl complex possesses a singlet ground state. The trismethyl fragments, on the other hand, have a ground state that evolves as a function of the ligand saturating the coordination sphere: a singlet for triflate and pyridine and a triplet for iodine, demonstrating the capacity for simple tuning of the electronic structure of these complexes. While the addition of B(CF) to the platinum + II bis methyl complex leads to FLP-like reactivity triggering THF opening, reactivity with [PhC][BPh] leads to oxidation of the bipym ligand. Furthermore, the light reactivity of the tetramethyl complex indicated the possible transfer of a methyl group, leading to functionalization of the bridging bipym ligand.

摘要

本文聚焦于镧系元素与铂的异双金属配合物的合成。它描述了Cp*Yb(bipym)PtMe配合物的合成及其表征,随后阐述了其与氧化剂的反应活性,从而得到各种含三甲基(PtMe)和四甲基(PtMe)片段的Pt + IV化合物。通过磁性测量对配合物电子性质的表征表明,四甲基配合物具有单重态基态。另一方面,三甲基片段的基态会随着使配位球饱和的配体而变化:对于三氟甲磺酸盐和吡啶为单重态,对于碘为三重态,这表明这些配合物的电子结构具有简单可调性。虽然向铂 + II双甲基配合物中添加B(CF)会引发类似FLP的反应活性从而导致四氢呋喃开环,但与[PhC][BPh]的反应会导致联吡啶配体被氧化。此外,四甲基配合物的光反应活性表明可能发生甲基转移,从而导致桥连联吡啶配体的官能化。

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