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Articles

Spectroscopic, structural, electrochemical, and cytotoxicity studies on dithiocarbamato-chelated ruthenium organometallics incorporating imine-phenol function

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Pages 180-200 | Received 12 Apr 2018, Accepted 13 Oct 2018, Published online: 12 Jan 2019
 

Abstract

The heterogeneous phase reaction of [Ru(η2-RL)(PPh3)2(CO)Cl] (1) with the sodium salts of dimethyl dithiocarbamate (MeDTC), diethyl dithiocarbamate (EtDTC), and pyrrolidine dithiocarbamate (PyrDTC) ligands led to the isolation of bright-yellow crystalline solids of type [Ru(η1-RL)(PPh3)2(CO)(R′DTC)] (2(R)(R′DTC)) where η2-RL is C6H2O-2-CHNHC6H4R(p)-3-Me-5, η1-RL is C6H2OH-2-CHNC6H4R(p)-3-Me-5, R is Me, OMe, Cl, and R = Me, Et, Pyr. The binding of dithiocarbamate ligand is accompanied by the dissociation of Ru-O and Ru-Cl bonds along with concomitant prototropic shift from iminium–phenolato to imine–phenol motif. The reaction also involves a sterically controlled change in rotational conformation in going to the products. The X-ray crystal structure of [Ru(η1-ClL)(PPh3)2(CO)(EtDTC)] (2(Cl)(EtDTC)) has been described here. An account of different spectral (UV–Vis, IR, NMR) and electrochemical data of the complexes are also asserted. Density functional theory (DFT) and time-dependent density functional theory (TD-DFT) analyses were performed to scrutinize the electronic structure and the absorption spectra of the complexes. One of the dithiocarbamato complexes has also been found to have in vitro antiproliferative properties against MDA-MB-231 breast cancer cell line which was determined by MTT assay. Cell death occurs mainly through apoptosis and flow cytometric analysis indicates that the complex induces cell cycle arrest in the sub G0/G1 phase.

GRAPHICAL ABSTRACT

Acknowledgments

M. K. G. and S. M. thank University Grants Commission (UGC), India, for the pre-doctoral fellowships. The support of DST-FIST and UGC-SAP to the Department of Chemistry are acknowledged.

Disclosure statement

No potential conflict of interest was reported by the authors.

Additional information

Funding

Financial supports from the Department of Science and Technology, Government of India (no. SR/S1/IC-65/2010) and the Council of Scientific & Industrial Research, New Delhi, India (no. 01(2898)/17/EMR-II) are gratefully acknowledged, University of Kalyani, for infrastructural facilities.

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