Tetrapyridineplatinum(II) Carboxylates: Synthesis and Crystal Structure

I. A. Yakushev; Якушев И. А.; M. Yu. Nesterenko; Нестеренко М. Ю.; P. V. Dorovatovskii; Дороватовский П. В.; A. B. Kornev; Корнев А. Б.; A. D. Maksimova; Максимова А. Д.; A. S. Popova; Попова А. С.; N. V. Cherkashina; Черкашина Н. В.; A. V. Churakov; Чураков А. В.; M. N. Vargaftik; Варгафтик М. Н.

doi:10.31857/S0132344X22700050

Tetrapyridineplatinum(II) Carboxylates: Synthesis and Crystal Structure

Authors: Yakushev I.A.¹, Nesterenko M.Y.¹^,2, Dorovatovskii P.V.³, Kornev A.B.⁴, Maksimova A.D.¹^,2, Popova A.S.¹^,5, Cherkashina N.V.¹, Churakov A.V.¹, Vargaftik M.N.¹
Affiliations:
1. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow, Russia
2. Higher Chemical College of the Russian Academy of Sciences, Mendeleev University of Chemical Technology of Russia, Moscow, Russia
3. National Research Center Kurchatov Institute, Moscow, Russia
4. Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow oblast, Russia
5. Peoples’ Friendship University of Russia, Moscow, Russia
Issue: Vol 49, No 1 (2023)
Pages: 51-63
Section: Articles
URL: https://journals.rcsi.science/0132-344X/article/view/137266
DOI: https://doi.org/10.31857/S0132344X22700050
EDN: https://elibrary.ru/ESOHZF
ID: 137266

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Abstract

A series of mono- and bimetallic cation-anionic complexes based on the [PtPy4]2+ cation with different single-charge anions of carboxylic acids (RCOO–) is synthesized and structurally characterized. A synthetic approach to the preparation of tetrapyridineplatinum complexes [PtPy4]2+ soluble in polar solvents from available reagents is developed. The reaction of tetrapyridineplatinum dichloride [PtPy4](Cl)2 with silver acetate or trifluoroacetate affords compounds [PtPy4](OOCMe)2·6H2O (I) and [PtPy4](OOCCF3)2· 2H2O (II) in the form of crystalline hydrates (CIF files CCDC nos. 2161100 and 2161101, respectively) in high yields. Other carboxylates can be prepared by the treatment of compound I with an excess of a stronger acid, for example, trifluoroacetic acid, with the formation of the corresponding complex trifluoroacetate [PtPy4](OOCCF3)2·4CF3COOH (IIa) (CIF file CCDC no. 2161102). Another method consists of the displacement of acetic acid with an excess of a lowly volatile acid, for example, pivalic acid, when [PtPy4](Piv)2· 5HPiv (III) is formed from the acid melt, and solvatomorph [PtPy4](Piv)2·4HPiv·3C6H12 (IIIa) (CIF files CCDC nos. 2161103 and 2161104, respectively) is formed in a cyclohexane medium. Heteroanionic heterometallic complex [PtPy4](OOCFc)(OOCMe) (IV) (CIF file CCDC no. 2161105) is shown to be formed by the reaction of complex I with ferrocenecarboxylic acid under mild conditions.

Keywords

platinum, cation-anionic complexes, crystalline hydrates, synthesis, X-ray diffraction analysis, crystal chemistry,

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