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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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organization
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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
  • scopus:84990050490
  • wos:000385161400025
ISSN
1477-9226
DOI
10.1039/c6dt02772e
language
English
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yes
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d644e63e-af77-453c-b75a-4ce01f9e66d2
date added to LUP
2017-02-08 11:04:01
date last changed
2017-10-29 04:57:39
@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},
  volume       = {45},
  year         = {2016},
}