Synthesis, structural insights and catalytic activity of a dioxidomolybdenum(VI) complex chelated with N 4 -(3-methoxyph
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Synthesis, structural insights and catalytic activity of a dioxidomolybdenum(VI) complex chelated with N4‑(3‑methoxyphenyl) thiosemicarbazone T. M. Asha1 · M. R. P. Kurup1,2 Received: 7 April 2020 / Accepted: 14 May 2020 © Springer Nature Switzerland AG 2020
Abstract A cis-dioxidomolybdenum(VI) complex of a thiosemicarbazone of the type [ MoO2L(DMSO)], where H 2L = 3-ethoxysalicylaldehyde-N4-(3-methoxyphenyl) thiosemicarbazone was synthesized. The molecular structure was determined by SCXRD analysis. The complex crystallizes in triclinic P1 space group. The structure consists of a distorted octahedral geometry around central metal, molybdenum. The various hydrogen bonding and 𝜋 ⋯ 𝜋 interactions were explored. Further, the nature and importance of these interactions in the crystal packing were revealed with the help of Hirshfeld surface analysis. Moreover, the synthesized compounds were characterized by physicochemical and spectroscopic methods. Redox properties of the compounds were analyzed by cyclic voltammetry. Finally, the molybdenum complex was evaluated for its catalytic potential for the oxidation of styrene and it displayed about 97% product selectivity for the oxidation of styrene to styrene oxide.
Introduction Thiosemicarbazones serve as excellent multidentate ligands that can coordinate with most of the transition metals forming complexes with varied structural features [1–4]. Similarly cis-dioxidomolybdenum(VI) complexes chelated with tridentate ONS donor ligands are of great importance in the domain of coordination chemistry owing to their ability to serve as model systems for the active site of the molybdoenzymes such as xanthine oxidase and sulfite oxidase [5, 6]. Moreover, the molybdenum complexes of thiosemicarbazones show excellent catalytic capacity related to the structural features of the coordinated cis-MoO2 unit, chelate ring structure and also substituents on the ligands [7, 8]. In addition to that, some of the molybdenum complexes also Electronic supplementary material The online version of this article (https://doi.org/10.1007/s11243-020-00398-5) contains supplementary material, which is available to authorized users. * M. R. P. Kurup [email protected]; [email protected] 1
Department of Applied Chemistry, Cochin University of Science and Technology, Kochi, Kerala 682 022, India
Department of Chemistry, School of Physical Sciences, Central University of Kerala, Tejaswini Hills, Periye, Kasargode, Kerala 671 320, India
2
catalyze oxygen atom transfer reactions [9, 10]. With the exception as being models of enzymatic active sites, molybdenum complexes of tridentate thiosemicarbazone ligands are important because of their potential catalytic activity [11, 12]. Herein, we report the synthesis and spectral characterization of a dioxidomolybdenum(VI) complex [ MoO2L(DMSO)] of a thiosemicarbazone ligand, H 2L reported by us [13], and having appropriate structure to catalyze oxidation as well as oxo-transfer reactions. The complex contains doubly deprotonated tridentate fo
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