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Solvent-Induced Formation of Novel Ni(II) Complexes Derived from Bis-Thiosemicarbazone Ligand: An Insight from Experimental and Theoretical Investigations.
Mahmoudi, Ghodrat; Babashkina, Maria G; Maniukiewicz, Waldemar; Afkhami, Farhad Akbari; Nunna, Bharath Babu; Zubkov, Fedor I; Ptaszek, Aleksandra L; Szczepanik, Dariusz W; Mitoraj, Mariusz P; Safin, Damir A.
Afiliação
  • Mahmoudi G; Department of Chemistry, Faculty of Science, University of Maragheh, Maragheh P.O. Box 55181-83111, Iran.
  • Babashkina MG; Independent Researcher, Respubliki Str. 14, 625003 Tyumen, Russia
  • Maniukiewicz W; Institute of General and Ecological Chemistry, Lodz University of Technology, Zeromskiego 116, 90-924 Lódz, Poland.
  • Afkhami FA; Department of Chemistry, The University of Alabama, Box 870336, 250 Hackberry Lane, Tuscaloosa, AL 35487, USA.
  • Nunna BB; Department of Mechanical and Industrial Engineering, New Jersey Institute of Technology, University Heights, Newark, NJ 07102, USA.
  • Zubkov FI; Department of Medicine, Division of Engineering in Medicine, Brigham and Women's Hospital, Harvard Medical School, Harvard University, Cambridge, MA 02139, USA.
  • Ptaszek AL; Organic Chemistry Department, Faculty of Science, Peoples' Friendship University of Russia (RUDN University), Miklukho-Maklaya Str. 6, 117198 Moscow, Russia.
  • Szczepanik DW; Department of Theoretical Chemistry, Faculty of Chemistry, Jagiellonian University, Gronostajowa 2, 30-387 Cracow, Poland.
  • Mitoraj MP; Department of Theoretical Chemistry, Faculty of Chemistry, Jagiellonian University, Gronostajowa 2, 30-387 Cracow, Poland.
  • Safin DA; Department of Theoretical Chemistry, Faculty of Chemistry, Jagiellonian University, Gronostajowa 2, 30-387 Cracow, Poland.
Int J Mol Sci ; 22(10)2021 05 19.
Article em En | MEDLINE | ID: mdl-34069455
In this work, we report solvent-induced complexation properties of a new N2S2 tetradentate bis-thiosemicarbazone ligand (H2LI), prepared by the condensation of 4-phenylthiosemicarbazide with bis-aldehyde, namely 2,2'-(ethane-1,2-diylbis(oxy)dibenzaldehyde, towards nickel(II). Using ethanol as a reaction medium allowed the isolation of a discrete mononuclear homoleptic complex [NiLI] (1), for which its crystal structure contains three independent molecules, namely 1-I, 1-II, and 1-III, in the asymmetric unit. The doubly deprotonated ligand LI in the structure of 1 is coordinated in a cis-manner through the azomethine nitrogen atoms and the thiocarbonyl sulfur atoms. The coordination geometry around metal centers in all the three crystallographically independent molecules of 1 is best described as the seesaw structure. Interestingly, using methanol as a reaction medium in the same synthesis allowed for the isolation of a discrete mononuclear homoleptic complex [Ni(LII)2] (2), where LII is a monodeprotonated ligand 2-(2-(2-(2-(dimethoxymethyl)phenoxy)ethoxy)benzylidene)-N-phenylhydrazine-1-carbothioamide (HLII). The ligand LII was formed in situ from the reaction of LI with methanol upon coordination to the metal center under synthetic conditions. In the structure of 2, two ligands LII are coordinated in a trans-manner through the azomethine nitrogen atom and the thiocarbonyl sulfur atom, also yielding a seesaw coordination geometry around the metal center. The charge and energy decomposition scheme ETS-NOCV allows for the conclusion that both structures are stabilized by a bunch of London dispersion-driven intermolecular interactions, including predominantly N-H∙∙∙S and N-H∙∙∙O hydrogen bonds in 1 and 2, respectively; they are further augmented by less typical C-H∙∙∙X (where X = S, N, O, π), CH∙∙∙HC, π∙∙∙π stacking and the most striking, attractive long-range intermolecular C-H∙∙∙Ni preagostic interactions. The latter are found to be determined by both stabilizing Coulomb forces and an exchange-correlation contribution as revealed by the IQA energy decomposition scheme. Interestingly, the analogous long-range C-H∙∙∙S interactions are characterized by a repulsive Coulomb contribution and the prevailing attractive exchange-correlation constituent. The electron density of the delocalized bonds (EDDB) method shows that the nickel(II) atom shares only ~0.8|e| due to the σ-conjugation with the adjacent in-plane atoms, demonstrating a very weak σ-metalloaromatic character.
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Texto completo: 1 Coleções: 01-internacional Base de dados: MEDLINE Assunto principal: Tiossemicarbazonas / Níquel Idioma: En Revista: Int J Mol Sci Ano de publicação: 2021 Tipo de documento: Article País de afiliação: Irã País de publicação: Suíça

Texto completo: 1 Coleções: 01-internacional Base de dados: MEDLINE Assunto principal: Tiossemicarbazonas / Níquel Idioma: En Revista: Int J Mol Sci Ano de publicação: 2021 Tipo de documento: Article País de afiliação: Irã País de publicação: Suíça