The Theoretical and Experimental Investigation of the Fluorinated Palladium β-Diketonate Derivatives: Structure and Physicochemical Properties

Molecules

Denis E. Tryakhov¹  Tamara V. Basova²  Svetlana I. Dorovskikh²  Natalia B. Morozova²  Alexander S. Sukhikh²  Irina V. Mirzaeva²  Darya D. Klyamer² 

[1]Chemistry Department, Materials Science Faculty, Novosibirsk State University, 2 Pirogova Str., 630090 Novosibirsk, Russia

[2]Nikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciences, 3 Acad. Lavrentiev Ave., 630090 Novosibirsk, Russia

关键词: palladium(II) β-diketonate derivatives;    crystal structure;    Hirshfeld surface analysis;    DFT calculations;    TG study;   

DOI  :  10.3390/molecules27072207

来源: DOAJ

【 摘 要 】

To search for new suitable Pd precursors for MOCVD/ALD processes, the extended series of fluorinated palladium complexes [Pd(CH₃CXCHCO(R))₂] with β-diketone [tfa−1,1,1-trifluoro-2,4-pentanedionato (1); pfpa−5,5,6,6,6-pentafluoro-2,4-hexanedionato (3); hfba−5,5,6,6,7,7,7-heptafluoro-2,4-heptanedionato (5)] and β-iminoketone [i-tfa−1,1,1-trifluoro-2-imino-4-pentanonato (2); i-pfpa−5,5,6,6,6-pentafluoro-2-imino-4-hexanonato (4); i-hfba-5,5,6,6,7,7,7-heptafluoro-2-imino-4-heptanonato (6)] ligands were synthesized with 70–80% yields and characterized by a set of experimental (SXRD, XRD, IR, NMR spectroscopy, TG) and theoretical (DFT, Hirshfeld surface analysis) methods. Solutions of Pd β-diketonates contained both cis and trans isomers, while only trans isomers were detected in the solutions of Pd β-iminoketonates. The molecules 2–6 and new polymorphs of complexes 3 and 5 were arranged preferentially in stacks, and the distance between molecules in the stack generally increased with elongation of the fluorine chain in ligands. The H…F contacts were the main ones involved in the formation of packages of molecules 1–2, and C…F, F…F, NH…F contacts appeared in the structures of complexes 4–6. The stability of complexes and their polymorphs in the crystal phases were estimated from DFT calculations. The TG data showed that the volatility differences between Pd β-iminoketonates and Pd β-diketonates were minimized with the elongation of the fluorine chain in the ligands.

【 授权许可】

Unknown