Synthesis and structures of a pincer-type rhodium(III) complex : Reactivity toward biomolecules
(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.
(Less)
- author
- Milutinović, Milan M. ; Bogojeski, Jovana V. ; Klisurić, Olivera ; Scheurer, Andreas ; Elmroth, Sofi K C LU and Bugarčić, Živadin D.
- organization
- publishing date
- 2016
- 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
- pmid:27722449
- wos:000385161400025
- 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
- 2024-08-18 15:05:34
@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 > GSH > l-Met > 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}}, }