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Updated: Jul 8, 2025

Thermochemical Studies of NiII and ZnII Ternary Complexes Using Ion Mobility-Mass Spectrometry
Published on: June 8, 2022
Temperature-Dependent Spontaneous Resolution of a Tetrahedral Chiral-at-Nickel(II) Complex under Supramolecular
Yuanfei Liu1, Hitoshi Ube1, Kenichi Endo1
1Department of Chemistry, Graduate School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
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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