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Half-sandwich arene ruthenium complexes exhibit versatile chemistry, serve as excellent precursors and find potential applications in many organic transformations. This review mainly focuses on the chemistry of piano-stool ruthenium complexes with special emphasis on the achiral or chiral-at-ruthenium center. Also, it deals with the synthesis, nomenclature and stereochemistry of arene ruthenium complexes along with mechanistic insights into the epimerization reactions and their applications in catalytic organic transformations with some selected examples.

The Schiff base ligands benzylidene­(4-tert-butylphenyl)­amine 4-methyl ester (L1), (4-nitrobenzylidene)­(4-tert-butylphenyl)­amine (L2), and (4-cyanobenzylidene)­(4-tert-butylphenyl)­amine (L3) and the new series of cyclometalated mononuclear piano-stool complexes [(η5-C5Me5)­RhCl­(L1)] (1), [(η5-C5Me5)­RhCl­(L2)] (2), [(η5-C5Me5)­RhCl­(L3)] (3), [(η5-C5Me5)­IrCl­(L1)] (4), [(η5-C5Me5)­IrCl­(L2)] (5), and [(η5-C5Me5)­IrCl­(L3)] (6) have been synthesized. The ligands L1–L3 and complexes 1–6 have been thoroughly characterized by satisfactory elemental analyses, spectral studies (ESI-MS, IR, 1H and 13C NMR, UV–vis), and structures of 1–3 authenticated by X-ray single-crystal analyses. Efficient binding of 1–6 with calf thymus DNA (CT DNA) have been established by UV–vis and emission spectroscopic studies. Protein binding (bovine serum albumin, BSA) has been investigated by UV–vis, fluorescence, synchronous, and 3D fluorescence spectroscopy. Binding of the complexes with DNA through minor groove and hydrophobic interaction with proteins via sub domain IIA cavity has been substantiated by molecular docking studies. The complexes exhibited significant cytotoxicity against the human lung cancer cell line (A549), and 1 and 2 showed better activity than cisplatin. The cytotoxicity, morphological changes, and apoptosis have been assessed by MTT assay, Hoechst 33342/PI staining, cell cycle analysis by fluorescence-activated cell sorting (FACS), and reactive oxygen species (ROS) generation by DCFH-DA dye. The complexes 1–6 induce apoptosis in the order 2 > 1 > 4 > 3 > 5 > 6.

Syntheses and characterizations of the arene ruthenium [(η(6)-C6H6)RuCl(4-mtdpm)] (1), [(η(6)-p-MeC6H4Pr(i))RuCl(4-mtdpm)] (2), and structurally analogous rhodium/iridium complexes [(η(5)-C5Me5)RhCl(4-mtdpm)] (3) and [(η(5)-C5Me5)IrCl(4-mtdpm)] (4) [4-mtdpm = 5-(4-methylthiophenyl)dipyrromethene] have been reported. Their identities have been established by satisfactory elemental analyses, electrospray ionization-mass spectrometry (ESI-MS), FT-IR, NMR ((1)H, (13)C), UV/vis, emission spectral, and electrochemical studies. Structure of the representative complex 3 has been authenticated by X-ray single crystal analyses. The complexes 1-4 effectively bind with calf thymus DNA (CT DNA) through intercalative/electrostatic interactions. In addition, these exhibit significant cytotoxicity toward Dalton lymphoma (DL) cell line and cause static quenching of the bovine serum albumin (BSA) fluorophore. The antiproliferative activity, morphological changes, and apoptosis have been evaluated by MTT assay, acridine orange/ethidium bromide (AO/EtBr) fluorescence staining, and DNA ladder assay. Mode of interaction of the complexes with DNA/protein has also been supported by molecular docking. Various studies revealed remarkable decrease in the in vitro DL cell proliferation and induction of the apoptosis by 1-4, which lies in the order 2 > 1 > 4 > 3.

Binuclear zinc(II) and copper(II) complexes based on a new Schiff base ligand N,N'-bis(2-hydroxybenzilidene)-2,4,6-trimethylbenzene-1,3-diamine (H(2)L) have been synthesized. The ligand H(2)L and complexes under investigation have been characterized by elemental analyses, spectral (FT-IR, (1)H, (13)C NMR, ESI-MS, electronic absorption, emission), and electrochemical studies. The structures of H(2)L and complexes [{Zn(C(23)H(18)N(2)O(2))}(2)] (1) and [{Cu(C(23)H(18)N(2)O(2))}(2)]·H(2)O (2) have been determined crystallographically. Selective "On-Off-On" switching behavior of the fluorescent complex 1 has been studied. The fluorescence intensity of 1 quenches (turns-off) upon addition of Cu(2+), while enhances (turns-on) in the presence of Ag(+) ions. The mechanisms of "On-Off-On" signaling have been supported by (1)H NMR, ESI-MS, electronic absorption, and emission spectral studies. Job's plot analysis supported 1:1 and 1:2 stoichiometries for Cu(2+) and Ag(+) ions, respectively. Association and quenching constants have been estimated by the Benesi-Hildebrand method and Stern-Volmer plot. Moreover, 1 mimics a molecular keypad lock that follows correct chemical input order to give maximum output signal.

The synthesis of four novel heteroleptic dipyrrinato complexes [(η(6)-arene)RuCl(2-pcdpm)] (η(6)-arene = C6H6, 1; C10H14, 2) and [(η(5)-C5Me5)MCl(2-pcdpm)] (M = Rh, 3; Ir, 4) containing a new chelating ligand 4-(2-methoxypyridyl)-phenyldipyrromethene (2-pcdpm) have been described. The complexes 1-4 have been fully characterized by various physicochemical techniques, namely, elemental analyses, spectral (ESI-MS, IR, (1)H, (13)C NMR, UV/vis) and electrochemical studies (cyclic voltammetry (CV) and differential pulse voltammetry (DPV)). Structures of 3 and 4 have been determined crystallographically. In vitro antiproliferative and cytotoxic activity of these complexes has been evaluated by trypan blue exclusion assay, cell morphology, apoptosis, acridine orange/ethidium bromide (AO/EtBr) fluorescence staining, and DNA fragmentation assay in Dalton lymphoma (DL) cell lines. Interaction of 1-4 with calf thymus DNA (CT DNA) has also been supported by absorption titration and electrochemical studies. Our results suggest that in vitro antitumor activity of 1-4 lies in the order 2 > 1 > 4 > 3.

The importance of Tinospora cordifolia stem and leaves extract was investigated for its possible hepatoprotective effect in Swiss albino male mice against lead nitrate induced toxicity. Oral administration of plant extracts prevented the occurrence of lead nitrate induced liver damage. The decreased level of tissue enzymes, i.e., superoxide dismutase (SOD), catalase (CAT) and increased level of aspartate aminotransferase (AST), alanine aminotransferase (ALT), alkaline phosphatase (ALP), and acid phosphatase (ACP) were observed in mice treated with lead. Administration of aqueous stem extract (400 mg/kg body weight, orally) and aqueous leaves extract (400 mg/kg body weight, orally) along with the lead nitrate (5 mg/kg body weight, i.p. for 30 days) increased the activities of SOD and CAT and decreased the levels of AST, ALT, ALP, and ACP enzymes in mice. These biochemical observations were supplemented by histopathology/histological examinations of liver section. Results of this study revealed that plant extract could afford protection against lead-induced hepatic damage.

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