Dataset Information

Isolation of Au-, Co-?¹PCO and Cu-?²PCO complexes, conversion of an Ir-?¹PCO complex into a dimetalladiphosphene, and an interaction-free PCO anion.

ABSTRACT: Sodium phosphaethynolate reacts with [MCl(PDI)] (M = Co, Ir; PDI = pyridinediimine) to give metallaphosphaketenes, which in the case of iridium rearranges into a dimetalladiphosphene, via CO migration from phosphorus to the metal. Two different bonding modes of the PCO anion to CAAC-coinage metal complexes [CAAC: cyclic (alkyl)(amino)(carbene)] are reported, one featuring a strong Au-P bond and the other an ?² coordination to copper. The gold complex appears to be mostly unreactive whereas the copper complex readily reacts with various organic substrates. A completely free PCO anion was structurally characterized as the [Cu(L_a)₂]⁺ (OCP)^- salt. It results from the simple displacement of the PCO unit of the cationic (CAAC)Cu(PCO) complex by a second equivalent of CAAC.

SUBMITTER: Liu L

PROVIDER: S-EPMC6003603 | biostudies-literature | 2016 Mar

REPOSITORIES: biostudies-literature

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Publications

Isolation of Au-, Co-η1PCO and Cu-η2PCO complexes, conversion of an Ir-η1PCO complex into a dimetalladiphosphene, and an interaction-free PCO anion.

Liu Liu L Ruiz David A DA Dahcheh Fatme F Bertrand Guy G Suter Riccardo R Tondreau Aaron M AM Grützmacher Hansjörg H

Chemical science 20160104 3

Sodium phosphaethynolate reacts with [MCl(PDI)] (M = Co, Ir; PDI = pyridinediimine) to give metallaphosphaketenes, which in the case of iridium rearranges into a dimetalladiphosphene, via CO migration from phosphorus to the metal. Two different bonding modes of the PCO anion to CAAC-coinage metal complexes [CAAC: cyclic (alkyl)(amino)(carbene)] are reported, one featuring a strong Au-P bond and the other an η2 coordination to copper. The gold complex appears to be mostly unreac ...[more]

PMID: 29997776

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Project description:The treatment of malignant cells that are deficient in oxygen due to the insufficient flow of blood is often seen as a major hindrance in radiotherapy. Such cells become radio-resistant because molecular oxygen, the natural and best radio-sensitizer, is depleted. Hence, to compensate this deficiency in oxygen, there is a need for agents that enhance radiation-induced damage of cells (radio-sensitizers) in a manner that normal cells are least affected. Simultaneously, agents capable of showing activity under hypoxic conditions are known as hypoxic cytotoxins that selectively and preferably destroy cells under hypoxic environments. 5-Nitroimidazoles fit both definitions. Their efficiency is based on their ability to generate the nitro radical anion that interacts with the strands of DNA within cells, either damaging or modifying them, leading to cell death. 5-Nitroimidazoles are important radio-pharmaceuticals (radio-sensitizers) in cancer-related treatments where the nitro radical anion has an important role. Since its generation leads to neurotoxic side effects that may be controlled through metal complex formation, this study looks at the possibility of two monomeric complexes of Ornidazole [1-chloro-3-(2-methyl-5-nitro-1H-imidazole-1-yl)propan-2-ol] with CuII and ZnII to be better radio-sensitizers and/or hypoxic cytotoxins than Ornidazole. The study reveals that although there is a decrease in nitro radical anion formation by complexes, such a decrease does not hamper their radio-sensitizing ability. Nucleic acid bases (thymine, cytosine, and adenine) or calf thymus DNA used as targets were irradiated with 60Co γ rays either in the absence or presence of Ornidazole and its monomeric complexes. Radiation-induced damage of nucleic acid bases was followed by high-performance liquid chromatography (HPLC), and modification of calf thymus DNA was followed by ethidium bromide fluorescence. Studies indicate that the complexes were better in performance than Ornidazole. CuII-ornidazole was significantly better than either Ornidazole or ZnII-ornidazole, which is attributed to certain special features of the CuII complex; aspects like having a stable lower oxidation state enable it to participate in Fenton reactions that actively influence radio-sensitization and the ability of the complex to bind effectively to DNA.

Dataset Information

Isolation of Au-, Co-?¹PCO and Cu-?²PCO complexes, conversion of an Ir-?¹PCO complex into a dimetalladiphosphene, and an interaction-free PCO anion.

Publications

Isolation of Au-, Co-η<sup>1</sup>PCO and Cu-η<sup>2</sup>PCO complexes, conversion of an Ir-η<sup>1</sup>PCO complex into a dimetalladiphosphene, and an interaction-free PCO anion.

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Dataset Information

Isolation of Au-, Co-?1PCO and Cu-?2PCO complexes, conversion of an Ir-?1PCO complex into a dimetalladiphosphene, and an interaction-free PCO anion.

Publications

Isolation of Au-, Co-η<sup>1</sup>PCO and Cu-η<sup>2</sup>PCO complexes, conversion of an Ir-η<sup>1</sup>PCO complex into a dimetalladiphosphene, and an interaction-free PCO anion.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets

Isolation of Au-, Co-?¹PCO and Cu-?²PCO complexes, conversion of an Ir-?¹PCO complex into a dimetalladiphosphene, and an interaction-free PCO anion.