Temperature-Dependent Spontaneous Resolution of a Tetrahedral Chiral-at-Nickel(II) Complex under Supramolecular Control

IF 3.3 Q2 CHEMISTRY, MULTIDISCIPLINARY ACS Organic & Inorganic Au Pub Date : 2023-09-07 DOI:10.1021/acsorginorgau.3c00026

Yuanfei Liu, Hitoshi Ube*, Kenichi Endo and Mitsuhiko Shionoya*,

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Abstract

Although stereochemical control of carbon centers is a well-established technique in modern synthetic chemistry, that of tetrahedral metal complexes with a stereogenic metal center remains difficult due to the dynamic nature of their coordination bonds. Here we report the synthesis of a tetrahedral d⁸ high-spin chiral-at-nickel(II) complex composed exclusively of achiral ligands and the supramolecular control of its temperature-dependent spontaneous resolution in crystals. Under certain conditions, complex molecules with the same absolute configuration of the nickel(II) center grow into conglomerate crystals with a helically arranged structure due to intermolecular hydrogen bonding. This process is highly spontaneous, does not require any chiral sources, and is closely related to the origin of homochirality in biological systems. The obtained enantiopure nickel(II) complex will be a new type of redox-active chiral source for asymmetric synthetic chemistry.

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在超分子控制下，四面体手性镍(II)配合物的温度依赖自发分解

虽然碳中心的立体化控制在现代合成化学中是一项成熟的技术，但由于配位键的动态性质，具有立体化中心的四面体金属配合物的立体化控制仍然很困难。本文报道了一种完全由非手性配体组成的四面体d8高自旋手性-镍(II)配合物的合成及其在晶体中随温度依赖的自发分辨率的超分子控制。在一定条件下，具有相同镍(II)中心绝对构型的复杂分子，由于分子间氢键作用，生长成具有螺旋排列结构的砾岩晶体。这个过程是高度自发的，不需要任何手性源，并且与生物系统中同手性的起源密切相关。该对映纯镍(II)配合物将成为不对称合成化学中一种新型的氧化还原活性手性源。

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ACS Organic & Inorganic Au 有机化学、无机化学-

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4.10

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0.00%

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期刊介绍： ACS Organic & Inorganic Au is an open access journal that publishes original experimental and theoretical/computational studies on organic organometallic inorganic crystal growth and engineering and organic process chemistry. Short letters comprehensive articles reviews and perspectives are welcome on topics that include:Organic chemistry Organometallic chemistry Inorganic Chemistry and Organic Process Chemistry.

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