Group 10 metal complexes with a tetradentate thiosemicarbazonate ligand: Synthesis, crystal structures and computational insights into the catalysis for C-C coupling via Mizoroki-Heck reaction

Author(s):Show less -

Lima, Jackelinne C. ^[1] ; Nascimento, Rebecca D. ^[2] ; Vilarinho, Luana M. ^[2] ; Borges, Alice P. ^[1] ; Silva, Leonardo H. F. ^[3] ; Souza, Jhonathan R. ^[3] ; Dinelli, Luis R. ^[2] ; Deflon, Victor M. ^[4] ; da Hora Machado, Antonio E. ^{[3, 5]} ; Bogado, Andre L. ^[2] ; Maia, Pedro I. S. ^[1]

Affiliation

^[1] Univ Fed Triangulo Mineiro, Dept Quim, Av Dr Randolfo Borges 1400, BR-38025440 Uberaba, MG - Brazil

^[2] Univ Fed Uberlandia, Inst Ciencias Exatas & Nat Pontal, Rua Vinte 1600, BR-38304402 Ituiutaba, MG - Brazil

^[3] Univ Fed Uberlandia, Inst Quim, Av Joao Naves de Avila 2121, BR-38400902 Uberlandia, MG - Brazil

^[4] Univ Sao Paulo, Inst Quim Sao Carlos, Av Trabalhador Saocarlense 400, BR-13566590 Sao Carlos, SP - Brazil

^[5] Univ Fed Catalao, Av Lamartine Pinto de Avelar 1120, BR-75704020 Catalao, Go - Brazil

• Document type: Journal article
• Source: Journal of Molecular Structure; v. 1199, JAN 5 2020.
• Web of Science Citations: 1

Abstract

A series of mononuclear complexes has been synthesized by reactions of group 10 metal ions with bis(4-phenyl-3-thiosemicarbazone) (H(2)bPht), affording compounds of general formula {[}M-II (bPht)] (M = Ni, Pd and Pt). Their characterization involved FTIR, UV-Vis, H-1 NMR, CV, DPV and elemental analysis. Furthermore, the crystal structures of all complexes have been determined, showing that the thio-semicarbazonate ligand is coordinated as a tetradentate N,N,S,S-donor forming three five-membered chelate rings. The catalytic activity of {[}M-II (bPht)] in Heck's C-C coupling reaction using styrene and iodobenzene to obtain stilbenes has been evaluated. It was verified that the Ni-II and Pt-II complexes present low catalytic activity, while the Pd-ll complex showed a conversion of 99% within 24 h. Transstilbene was identified as the major product of the coupling reaction, up to 90%. DFT studies were also performed in order to better understand the catalytic behavior of these complexes giving support for a new route for Mizoroki-Heck reaction. (C) 2019 Elsevier B.V. All rights reserved. (AU)

• FAPESP's process: 09/54011-8 - Acquisition of a single-crystal X-ray diffractometer for the structural analysis of small molecules and proteins
• Grantee: Victor Marcelo Deflon
• Support Opportunities: Multi-user Equipment Program