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

A novel rhodium( iii ) complex [Rh III (H 2 L t Bu )Cl 3 ] ( 1 ) (H 2 L t Bu = 2,6-bis(5- tert -butyl-1 H -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 orthorhomb...

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Veröffentlicht in:Dalton transactions : an international journal of inorganic chemistry 2016-01, Vol.45 (39), p.15481-15491
Hauptverfasser: Milutinovi, Milan M, Bogojeski, Jovana V, Klisuri, Olivera, Scheurer, Andreas, Elmroth, Sofi K. C, Bugar i, ivadin D
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container_end_page 15491
container_issue 39
container_start_page 15481
container_title Dalton transactions : an international journal of inorganic chemistry
container_volume 45
creator Milutinovi, Milan M
Bogojeski, Jovana V
Klisuri, Olivera
Scheurer, Andreas
Elmroth, Sofi K. C
Bugar i, ivadin D
description A novel rhodium( iii ) complex [Rh III (H 2 L t Bu )Cl 3 ] ( 1 ) (H 2 L t Bu = 2,6-bis(5- tert -butyl-1 H -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 3 , and eight molecules in the unit cell. The rhodium center in the complex [Rh III (H 2 L t Bu )Cl 3 ] ( 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 III 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 III (H 2 L t Bu )Cl 3 ] 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. A novel Rh III complex containing a pincer type nitrogen-donor ligand was synthesized; its interaction toward small biomolecules, duplex DNAs and RNA as well as CT-DNA and BSA was investigated.
doi_str_mv 10.1039/c6dt02772e
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C ; Bugar i, ivadin D</creator><creatorcontrib>Milutinovi, Milan M ; Bogojeski, Jovana V ; Klisuri, Olivera ; Scheurer, Andreas ; Elmroth, Sofi K. C ; Bugar i, ivadin D</creatorcontrib><description>A novel rhodium( iii ) complex [Rh III (H 2 L t Bu )Cl 3 ] ( 1 ) (H 2 L t Bu = 2,6-bis(5- tert -butyl-1 H -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 3 , and eight molecules in the unit cell. The rhodium center in the complex [Rh III (H 2 L t Bu )Cl 3 ] ( 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 III 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 III (H 2 L t Bu )Cl 3 ] 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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C</creatorcontrib><creatorcontrib>Bugar i, ivadin D</creatorcontrib><title>Synthesis and structures of a pincer-type rhodium() complex: reactivity toward biomolecules</title><title>Dalton transactions : an international journal of inorganic chemistry</title><addtitle>Dalton Trans</addtitle><description>A novel rhodium( iii ) complex [Rh III (H 2 L t Bu )Cl 3 ] ( 1 ) (H 2 L t Bu = 2,6-bis(5- tert -butyl-1 H -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 3 , and eight molecules in the unit cell. The rhodium center in the complex [Rh III (H 2 L t Bu )Cl 3 ] ( 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 III 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 III (H 2 L t Bu )Cl 3 ] 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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C</au><au>Bugar i, ivadin D</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Synthesis and structures of a pincer-type rhodium() complex: reactivity toward biomolecules</atitle><jtitle>Dalton transactions : an international journal of inorganic chemistry</jtitle><addtitle>Dalton Trans</addtitle><date>2016-01-01</date><risdate>2016</risdate><volume>45</volume><issue>39</issue><spage>15481</spage><epage>15491</epage><pages>15481-15491</pages><issn>1477-9226</issn><eissn>1477-9234</eissn><abstract>A novel rhodium( iii ) complex [Rh III (H 2 L t Bu )Cl 3 ] ( 1 ) (H 2 L t Bu = 2,6-bis(5- tert -butyl-1 H -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 3 , and eight molecules in the unit cell. The rhodium center in the complex [Rh III (H 2 L t Bu )Cl 3 ] ( 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 III 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 III (H 2 L t Bu )Cl 3 ] 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. A novel Rh III complex containing a pincer type nitrogen-donor ligand was synthesized; its interaction toward small biomolecules, duplex DNAs and RNA as well as CT-DNA and BSA was investigated.</abstract><cop>England</cop><pmid>27722449</pmid><doi>10.1039/c6dt02772e</doi><tpages>11</tpages><orcidid>https://orcid.org/0000-0002-2858-9406</orcidid><oa>free_for_read</oa></addata></record>
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source MEDLINE; Royal Society Of Chemistry Journals; Alma/SFX Local Collection
subjects Biomolecules
Chelating Agents - chemistry
Chemical Sciences
Coordination Complexes - chemical synthesis
Coordination Complexes - chemistry
Coordination compounds
Crystallography, X-Ray
Deoxyribonucleic acid
DNA - chemistry
Glutathione - chemistry
Guanosine Monophosphate - chemistry
Histidine - chemistry
Inorganic Chemistry
Kemi
Kinetics
Ligands
Methionine - chemistry
Models, Molecular
Molecular Structure
Natural Sciences
Naturvetenskap
Nitrogen atoms
Oorganisk kemi
Protein Binding
Rhodium - chemistry
Ribonucleic acids
Serum Albumin, Bovine - chemistry
Synthesis
Unit cell
title Synthesis and structures of a pincer-type rhodium() complex: reactivity toward biomolecules
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