Complete synthetic, structural, and biomedical studies of two Pd complexes as well as Au and Ag complexes of 1-benzyl-3-tert-butylimidazol-2-ylidene are reported. Specifically, trans-[1-benzyl-3-tert-butylimidazol-2-ylidene]Pd(pyridine)Cl2 (1a) was synthesized from the reaction of 1-benzyl-3-tert-butylimidazolium chloride (1) with PdCl2 in the presence of K2CO3 as a base. The other palladium complex, [1-benzyl-3-tert-butylimidazol-2-ylidene]2PdCl2 (1b), and a gold complex, [1-benzyl-3-tert-butylimidazol-2-ylidene]AuCl (1c), were synthesized by following a transmetallation route from the silver complex, [1-benzyl-3-tert-butylimidazol-2-ylidene]AgCl (1d), by treatment with (COD)PdCl2 and (SMe2)AuCl, respectively. The silver complex 1d in turn was synthesized by the reaction of 1 with Ag2O. The molecular structures of 1a-d have been determined by X-ray diffraction studies. Biomedical studies revealed that, while the palladium complexes 1a and 1b displayed potent anticancer activity, the gold (1c) and silver (1d) complexes exhibited significant antimicrobial properties. Specifically, 1b showed strong antiproliferative activity against three types of human tumor cells, namely, cervical cancer (HeLa), breast cancer (MCF-7), and colon adenocarcinoma (HCT 116), in culture. The antiproliferative activity of 1b was found to be considerably stronger than that of cisplatin. The 1b complex inhibited tumor cell proliferation by arresting the cell cycle progression at the G2 phase, preventing the mitotic entry of the cell. We present evidence suggesting that the treated cells underwent programmed cell death through a p53-dependent pathway. Though both the gold (1c) and silver (1d) complexes showed antimicrobial activity toward Bacillus subtilis, 1c was found to be ca. 2 times more potent than 1d.
Synthesis, structure, bonding, and photoluminescence studies of a pair of neutral dimeric silver and gold complexes of a N/O-functionalized N-heterocyclic carbene ligand exhibiting closed-shell d10...d10 argentophilic and aurophilic interactions, are reported. In particular, dimeric complexes of the type {[1-(benzyl)-3-(N-tert-butylacetamido)imidazol-2-ylidene]MCl}2 [M = Ag (2); Au (3)] displayed attractive metallophilic interaction in the form of a close ligand-unsupported metal...metal contact [3.1970(12) A in 2; 3.2042(2) A in 3] as observed from X-ray diffraction study and also was further verified by low temperature photoluminescence study at 77 K that showed the characteristic emission [527 nm for 2; 529 nm for 3] owing to the metal...metal interaction. The nature of the metallophilic interaction in these complexes was further probed using computational studies that estimated the metal...metal interaction energy to be 12.8 (2) and 8.6 kcal/mol (3). Notably, the argentophilic interaction was found to be stronger than the aurophilic interaction in this series of neutral dimeric complexes. The complexes 2 and 3 were synthesized sequentially, with the silver 2 complex prepared by the reaction of the 1-(benzyl)-3-(N-tert-butylacetamido)imidazolium chloride with Ag2O in 66% yield, while the gold 3 complex was obtained by the transmetallation reaction of the silver 2 complex with (SMe2)AuCl in 86% yield.
The in vogue N-heterocyclic carbenes (NHCs) have attracted attention largely for its new found popularity in chemical catalysis and also for displaying promising traits in biomedical applications. The current perspective provides an account of our efforts in exploring the utility of N/O-functionalized N-heterocyclic carbenes in these two areas. On the catalysis front, we have employed the N/O-functionalized N-heterocyclic carbene based precatalysts for the C-C and C-N bond forming reactions like the Suzuki-Miyaura, Sonogashira and Hiyama cross-couplings, the base-free Michael addition, the alkene and alkyne hydroamination reactions and the ring-opening polymerization (ROP) of L-lactides that produce biodegradable polylactide polymers while on the biomedical application front, the anticancer and antimicrobial properties of these N/O-functionalized N-heterocyclic carbene complexes were evaluated. Towards this objective, the N-heterocyclic carbene chemistry of a variety of transition metals like Ag, Au, Ni and Pd has been investigated.
The homopolymerization and the copolymerization of ethylene with functionalized 5-norbornen-2-yl derivatives by the nickel catalyst system L(and Ni(COD)2 (bis(1,5-cyclooctadiene)nickel) produces polymers with high molecular weights and narrow molecular weight distributions. A typical ethylene polymerization reaction proceeds under 100 psi of ethylene and at 20 °C, using 1 (0.34 mM) and Ni(COD)2 (0.83 mM). Likewise, under similar conditions, the copolymerization of ethylene with 5-norbornen-2-yl acetate (3) (0.15 M) for 90 min by 1 (0.67 mM) and Ni(COD)2 (1.67 mM) produced a high molecular weight functionalized polyethylene bearing ester functionalities. 5-Norbornen-2-ol (0.15 M) underwent a similar copolymerization with ethylene for 20 min to yield a hydroxy-functionalized polyethylene. Narrow molecular weight distributions, coupled with the increase of polymer molar mass with time, are consistent with a quasi-living polymerization process in the case of ethylene homopolymerization and ethylene copolymerization with 3.
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