Regioselective ligand substitution in square-planar Pt(II) complexes bearing N^C and C^C chelating ligands with pyrazole derivatives

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Inorganica Chimica Acta Pub Date : 2024-08-25 DOI:10.1016/j.ica.2024.122345

Yiming Yang , Sangjoon Moon , Shinnosuke Horiuchi , Kenichiro Omoto , Eri Sakuda , Yasuhiro Arikawa , Keisuke Umakoshi

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Abstract

The regioselectivity of the ligand substitution reaction of square-planar Pt(II) complexes with chelating ligands pyridyl-NHC (Py-NHC), phenyl-NHC (Ph-NHC), and phenyl-pyridine (ppy, Ph-Py) was studied. The reaction of the dichlorido Pt(II) complex bearing these chelating ligands in the presence of pyrazole (pz) ligands afforded mono-pyrazole adducts [PtCl(ChL)(pz)]ⁿ⁺ (n = 0 and 1; ChL=chelating ligand (Py-NHC, Ph-NHC, Ph-py)). The structures of the PtCl(pz) complexes with the Py-NHC, Ph-NHC, and Ph-Py chelating ligands were confirmed by X-ray crystallographic analysis. The regioselectivity of the ligand substitution reaction between the pyrazole moieties and chloride ions can be controlled by the strength of the trans effect of the chelating ligands. Based on the structures of the products, a clear trend of Py < NHC < Ph was observed in the trans effect of the chelating ligands. This finding provides a rational synthetic procedure for asymmetric Pt(II) complexes with chelating ligands in a stepwise manner.

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带有 N^C 和 C^C 螯合配体的方形平面铂(II)配合物与吡唑衍生物的区域选择性配体置换

研究了方形平面铂(II)配合物与螯合配体吡啶-NHC（Py-NHC）、苯基-NHC（Ph-NHC）和苯基吡啶（ppy，Ph-Py）发生配体置换反应的区域选择性。含有这些螯合配体的二氯铂（II）配合物在吡唑（pz）配体存在下的反应生成了单吡唑加合物 [PtCl(ChL)(pz)]n+（n = 0 和 1；ChL=螯合配体（Py-NHC、Ph-NHC、Ph-Py））。带有 Py-NHC、Ph-NHC 和 Ph-Py 螯合配体的 PtCl(pz) 复合物的结构已通过 X 射线晶体学分析得到证实。螯合配体反式效应的强弱可控制吡唑分子与氯离子之间配体取代反应的区域选择性。根据产物的结构，可以观察到螯合配体的反式效应有明显的 Py < NHC < Ph 趋势。这一发现为逐步合成具有螯合配体的不对称铂(II)配合物提供了合理的合成程序。

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来源期刊

Inorganica Chimica Acta 化学-无机化学与核化学

CiteScore

6.00

自引率

3.60%

发文量

440

审稿时长

35 days

期刊介绍： Inorganica Chimica Acta is an established international forum for all aspects of advanced Inorganic Chemistry. Original papers of high scientific level and interest are published in the form of Articles and Reviews. Topics covered include: • chemistry of the main group elements and the d- and f-block metals, including the synthesis, characterization and reactivity of coordination, organometallic, biomimetic, supramolecular coordination compounds, including associated computational studies; • synthesis, physico-chemical properties, applications of molecule-based nano-scaled clusters and nanomaterials designed using the principles of coordination chemistry, as well as coordination polymers (CPs), metal-organic frameworks (MOFs), metal-organic polyhedra (MPOs); • reaction mechanisms and physico-chemical investigations computational studies of metalloenzymes and their models; • applications of inorganic compounds, metallodrugs and molecule-based materials. Papers composed primarily of structural reports will typically not be considered for publication.