The constitutional dynamic chemistry of Au3(pyrazolate)3 complexes

IF 3.3 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions Pub Date : 2025-08-13 DOI:10.1039/D5DT01613D

Noga Eren, Renata Svecova, Farzaneh Fadaei-Tirani, Rosario Scopelliti and Kay Severin

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Abstract

Trinuclear Au₃(Pz)₃ complexes (Pz = pyrazolate) have been used extensively as components in molecular and polymeric nanostructures. However, the constitutional dynamic chemistry of Au₃(Pz)₃ complexes remains largely unexplored. We have investigated exchange reactions between Au₃(Pz)₃ complexes and pyrazole ligands in homogeneous solution. At room temperature and at low millimolar concentrations, several days were needed to establish the thermodynamic equilibrium. The slow exchange kinetics corroborate the inert character of Au₃(Pz)₃ complexes. When 3,5-diisopropylpyrazolato or 3,5-diphenylpyrazolato ligands were replaced by 3,5-bis(trifluoromethyl)pyrazolato ligands, a sigmoidal rate profile was observed. This observation led to the discovery that pyrazoles can act as potent (auto)catalysts for ligand exchange and ligand scrambling reactions with Au₃(Pz)₃ complexes. The kinetic studies were supplemented by crystallographic analyses of four heteroleptic Au₃(Pz)₂(Pz′) complexes.

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金（吡唑酸）3配合物的结构动力学化学

三核Au3(Pz)3配合物（Pz = pyrazolate）已广泛用作分子和聚合物纳米结构的组成部分。然而，Au3(Pz)3配合物的结构动态化学仍未得到充分的研究。研究了Au3(Pz)3配合物与吡唑配体在均相溶液中的交换反应。在室温和低毫摩尔浓度下，建立热力学平衡需要几天的时间。缓慢的交换动力学证实了Au3(Pz)3配合物的惰性特性。当3,5-二异丙基吡唑啉配体或3,5-二苯基吡唑啉配体被3,5-双（三氟甲基）吡唑啉配体取代时，观察到s型速率分布。这一发现导致吡唑可以作为配体交换和配体与Au3(Pz)3配合物的置乱反应的有效（自）催化剂。动力学研究补充了四种异电性Au3(Pz)2（Pz’）配合物的晶体学分析。

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来源期刊

Dalton Transactions 化学-无机化学与核化学

CiteScore

6.60

自引率

7.50%

发文量

1832

审稿时长

1.5 months

期刊介绍： Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.