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Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework
Published on: April 9, 2018
Reversible RS-NO bond cleavage and formation at copper(I) thiolates
Marie M Melzer1, Ercheng Li, Timothy H Warren
1Department of Chemistry, Georgetown University, Box 571227, Washington, DC 20057-1227, USA.
Copper(I) thiolates facilitate swift, reversible transnitrosation with S-nitrosothiols (RSNOs). These reactions do not trigger the release of nitric oxide gas from biological NO carriers.
Area of Science:
- Inorganic Chemistry
- Bioinorganic Chemistry
- Nitric Oxide Chemistry
Background:
- S-nitrosothiols (RSNOs) are crucial biological nitric oxide (NO) carriers.
- Understanding the chemistry of NO transfer is vital for biological applications.
- Copper complexes are known to interact with NO-related species.
Purpose of the Study:
- To investigate the transnitrosation reactivity of two-coordinate copper(I) thiolates with S-nitrosothiols.
- To determine if these copper complexes catalyze the decomposition of S-nitrosothiols.
- To elucidate the mechanism of NO transfer between copper thiolates and RSNOs.
Main Methods:
- Synthesis and characterization of two-coordinate copper(I) thiolates (IPrCu-SR).
- Reaction studies with various S-nitrosothiols (RSNOs).
- Spectroscopic monitoring (e.g., UV-Vis, NMR) to track reaction progress and identify intermediates.
Main Results:
- Two-coordinate copper(I) thiolates (IPrCu-SR) undergo rapid and reversible transnitrosation with RSNOs.
- The transnitrosation process does not lead to the catalytic release of nitric oxide gas (NO).
- Evidence suggests a direct transfer of the nitrosyl group (NO+) from sulfur to copper.
Conclusions:
- Two-coordinate copper(I) thiolates are effective reagents for reversible NO transfer from RSNOs.
- These complexes offer a controlled method for manipulating NO carriers without NO gas loss.
- The findings have implications for developing new strategies in NO-based therapeutics and chemical biology.
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