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Related Experiment Videos

Osmium Hydrazido and Dinitrogen Complexes.

George M. Coia1, Martin Devenney, Peter S. White

  • 1Chemistry Section, Laboratory of Comparative Carcinogenesis, National Cancer Institute, Frederick Cancer Research and Development Center, Frederick, Maryland 21702.

Inorganic Chemistry
|May 21, 1997
PubMed
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Materials (Basel, Switzerland)·2021
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Isolation and Characterization of the Osmium(V)-Imido Complex [Os(V)(Tp)(Cl)(2)(NH)] We are grateful to the National Science Foundation under Grant number CHE-9503738, the Los Alamos National Laboratory (DOE) under Grant Number 10730-001-00-2C, and the Laboratory Directed Research and Development Program for support of this research. M. H. V. Huynh gratefully acknowledges postdoctoral fellowship support from the Directorapos;s Office of Los Alamos National Laboratory. Los Alamos National Laboratory is operated by the University of California for the U.S. Department of Energy under Contract W-7405-ENG-36. We also thank Dr. Paul R. Sharp (Professor of Chemistry, University of Missouri, Columbia, MO, 65211) for the information on transition metal parent imido complexes.

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Medium Effects on Charge Transfer in Metal Complexes.

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Localization in trans,trans-[(tpy)(Cl)(2)Os(III)(N(2))Os(II)(Cl)(2)(tpy)](+) (tpy = 2,2':6',2"-Terpyridine).

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Preparation and Photophysical Properties of Amide-Linked, Polypyridylruthenium-Derivatized Polystyrene.

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This study details the electrochemical oxidation of an osmium complex with amines, forming new hydrazido complexes. These complexes exhibit bent coordination and undergo reversible redox reactions, providing insights into osmium-amine chemistry.

Area of Science:

  • Inorganic Chemistry
  • Electrochemistry
  • Coordination Chemistry

Background:

  • Osmium complexes with polypyridyl ligands are of interest for their redox properties.
  • Understanding the reactivity of osmium complexes with amines is crucial for developing new catalytic systems.

Purpose of the Study:

  • To investigate the electrochemical oxidation of [Os(tpy)(bpy)(NH3)](PF6)2 (1) in the presence of various amines.
  • To characterize the resulting osmium-amine complexes, including their structures and redox behavior.

Main Methods:

  • Electrochemical oxidation and reduction in aqueous and non-aqueous solutions.
  • X-ray crystallography for structural determination.
  • Cyclic voltammetry for kinetic studies.

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Main Results:

  • Oxidation of complex 1 with secondary aliphatic amines yielded [Os(tpy)(bpy)(NNR2)](PF6)3 (3) (n=4.6-5.0).
  • Complex 3 was reduced to [Os(tpy)(bpy)(NNR2)](PF6)2 (2) (n=1.0), with bent hydrazido(2-) coordination observed in crystal structures.
  • Protonation of 2 yielded hydrazido(1-) complexes, and reduction of 2 at low pH produced complex 1.

Conclusions:

  • The study elucidates the electrochemical pathways for osmium-amine complex formation and transformation.
  • The characterized hydrazido complexes demonstrate rich redox chemistry and structural features.
  • This work contributes to the understanding of osmium coordination chemistry and its potential applications.