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

Milutinović, Milan M. ; Bogojeski, Jovana V. ; Klisurić, Olivera ; Scheurer, Andreas ; Elmroth, Sofi K C LU and Bugarčić, Živadin D. (2016) In Dalton Transactions 45(39). p.15481-15491
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) Å, V = 2488.80(15) Å3, 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... (More)

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) Å, V = 2488.80(15) Å3, 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.

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publishing date
type
Contribution to journal
publication status
published
subject
in
Dalton Transactions
volume
45
issue
39
pages
11 pages
publisher
Royal Society of Chemistry
external identifiers
  • pmid:27722449
  • wos:000385161400025
  • scopus:84990050490
ISSN
1477-9226
DOI
10.1039/c6dt02772e
language
English
LU publication?
yes
id
d644e63e-af77-453c-b75a-4ce01f9e66d2
date added to LUP
2017-02-08 11:04:01
date last changed
2024-02-29 08:17:02
@article{d644e63e-af77-453c-b75a-4ce01f9e66d2,
  abstract     = {{<p>A novel rhodium(iii) complex [Rh<sup>III</sup>(H<sub>2</sub>L<sup>tBu</sup>)Cl<sub>3</sub>] (1) (H<sub>2</sub>L<sup>tBu</sup> = 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) Å, V = 2488.80(15) Å<sup>3</sup>, and eight molecules in the unit cell. The rhodium center in the complex [Rh<sup>III</sup>(H<sub>2</sub>L<sup>tBu</sup>)Cl<sub>3</sub>] (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 Rh<sup>III</sup> 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 &gt; GSH &gt; l-Met &gt; l-His. Duplex RNA reacts faster with the [Rh<sup>III</sup>(H<sub>2</sub>L<sup>tBu</sup>)Cl<sub>3</sub>] 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.</p>}},
  author       = {{Milutinović, Milan M. and Bogojeski, Jovana V. and Klisurić, Olivera and Scheurer, Andreas and Elmroth, Sofi K C and Bugarčić, Živadin D.}},
  issn         = {{1477-9226}},
  language     = {{eng}},
  number       = {{39}},
  pages        = {{15481--15491}},
  publisher    = {{Royal Society of Chemistry}},
  series       = {{Dalton Transactions}},
  title        = {{Synthesis and structures of a pincer-type rhodium(III) complex : Reactivity toward biomolecules}},
  url          = {{http://dx.doi.org/10.1039/c6dt02772e}},
  doi          = {{10.1039/c6dt02772e}},
  volume       = {{45}},
  year         = {{2016}},
}