Synthesis and structures of a pincer-type rhodium(III) complex: Reactivity toward biomolecules

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title = "Synthesis and structures of a pincer-type rhodium(III) complex: Reactivity toward biomolecules",
abstract = "A novel rhodium(iii) complex [RhIII(H2LtBu)Cl3] (1) (H2LtBu = 2,6-bis(5-tert-butyl-1H-pyrazol-3-yl)pyridine) containing a pincer type, tridentate nitrogen-donor chelate system was synthesized. Single crystal X-ray structure analysis revealed that 1 crystallizes in the orthorhombic space group Pbcn with a = 20.7982(6), b = 10.8952(4), c = 10.9832(4) {\AA}, V = 2488.80(15) {\AA}3, and eight molecules in the unit cell. The rhodium center in the complex [RhIII(H2LtBu)Cl3] (1) is coordinated in a slightly distorted octahedral geometry by the tridentate N,N,N-donor and three chloro ligands, adopting a mer arrangement with an essentially planar ligand skeleton. Due to the tridentate coordination of the N,N,N-donor, the central nitrogen atom N1 is located closer to the RhIII center. The reactivity of the synthesized complex toward small biomolecules (l-methionine (l-Met), guanosine-5′-monophosphate (5′-GMP), l-histidine (l-His) and glutathione (GSH)) and to a series of duplex DNAs and RNA was investigated. The order of reactivity of the studied small biomolecules is: 5′-GMP > GSH > l-Met > l-His. Duplex RNA reacts faster with the [RhIII(H2LtBu)Cl3] complex than duplex DNA, while shorter duplex DNA (15mer GG) reacts faster compared with 22mer GG duplex DNA. In addition, a higher reactivity is achieved with a DNA duplex with a centrally located GG-sequence than with a 22GTG duplex DNA, in which the GG-sequence is separated by a T base. Furthermore, the interaction of this metal complex 1 with calf thymus DNA (CT-DNA) and bovine serum albumin (BSA) was examined by absorption (UV-Vis) and emission spectral studies (EthBr displacement studies). Overall, the studied complex exhibited good DNA and BSA interaction ability.",
author = "Milutinovi{\'c}, {Milan M.} and Bogojeski, {Jovana V.} and Olivera Klisuri{\'c} and Andreas Scheurer and Elmroth, {Sofi K C} and Bugar{\v c}i{\'c}, {{\v Z}ivadin D.}",
year = "2016",
doi = "10.1039/c6dt02772e",
language = "English",
volume = "45",
pages = "15481--15491",
journal = "Dalton Transactions",
issn = "1477-9234",
publisher = "Royal Society of Chemistry",
number = "39",