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Formation and Redox Reactivity of Osmium(II) Thionitrosyl Complexes
El-Sayed El-Samanody1, Konstantinos D. Demadis, Laurie A. Gallagher
1Department of Chemistry, Venable and Kenan Laboratories, CB 3290, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599-3290, and Nalco Chemical Company, Global Water Research, One Nalco Center, Naperville, Illinois 60563-1198.
Inorganic Chemistry
|October 24, 2001
Summary
Osmium complexes react with carbon disulfide and azide to form thionitrosyl complexes. The thionitrosyl group exhibits diverse reactivity, undergoing S-atom transfer, reduction, and O-atom transfer reactions, yielding various osmium compounds.
Area of Science:
- Inorganic Chemistry
- Organometallic Chemistry
Background:
- Osmium complexes with tris(1-pyrazolyl)methane (tpm) and hydrotris(1-pyrazolyl)borate (Tp) ligands are known.
- The reactivity of osmium-nitrogen bonds is an area of ongoing research.
Purpose of the Study:
- To synthesize and characterize novel osmium thionitrosyl complexes.
- To investigate the reactivity of the thionitrosyl ligand in osmium complexes.
Main Methods:
- Synthesis of osmium thionitrosyl complexes via reaction with CS(2) and N(3)(-).
- Characterization of complexes using spectroscopic and electrochemical methods.
- Investigation of reactivity through reactions with PPh(3), reducing agents, and O=NMe(3).
Main Results:
- Successful synthesis of osmium thionitrosyl complexes [Os(VI)(tpm)(Cl)(2)(NS)](PF(6)) and [Os(II)(tpm)(Cl)(2)(NS)](BF(4)).
- Demonstrated S-atom transfer, reduction to ammine complexes, and O-atom transfer reactions of the thionitrosyl ligand.
- Observed competitive NO(+)/NS(+) exchange and S(2)(-) transfer in reactions with NO(+).
Conclusions:
- The thionitrosyl ligand in osmium complexes displays versatile reactivity.
- These findings expand the known chemistry of osmium-nitrogen and osmium-sulfur compounds.