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The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
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Dinitrogen complexes supported by tris(phosphino)silyl ligands.

Matthew T Whited1, Neal P Mankad, Yunho Lee

  • 1Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.

Inorganic Chemistry
|February 13, 2009
PubMed
Summary

The novel tris(phosphino)silyl ligand facilitates the creation of unique iron, cobalt, nickel, and iridium coordination complexes. These complexes include the first terminal dinitrogen adducts of monovalent iron, offering new avenues for chemical research.

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Published on: October 18, 2019

Area of Science:

  • Organometallic chemistry
  • Coordination chemistry
  • Inorganic chemistry

Background:

  • The development of novel ligands is crucial for advancing coordination chemistry and catalysis.
  • Tetradentate ligands offer unique coordination environments for metal centers.
  • Silyl-based ligands provide distinct electronic and steric properties.

Purpose of the Study:

  • To synthesize and characterize novel coordination complexes using the tetradentate tris(phosphino)silyl ligand, [SiP(iPr)(3)].
  • To explore the complexation behavior of this ligand with various transition metals, including iron, cobalt, nickel, and iridium.
  • To investigate the properties of resulting dinitrogen adducts and their potential for group transfer studies.

Main Methods:

  • Synthesis of the [SiP(iPr)(3)] ligand.
  • Coordination of the ligand with iron, cobalt, nickel, and iridium precursors.
  • Characterization of the resulting complexes using techniques such as X-ray crystallography, NMR spectroscopy, and electrochemistry.
  • Oxidation of dinitrogen adducts to form triflate complexes.

Main Results:

  • Successful preparation and characterization of divalent trigonal bipyramidal metal chlorides ([SiP(iPr)(3)]M-Cl) and monovalent dinitrogen adducts ([SiP(iPr)(3)]M-N(2)).
  • Discovery of the first terminal dinitrogen adducts of monovalent iron, featuring a trans-disposed silyl donor.
  • Synthesis of divalent iron and trivalent cobalt triflate complexes, [SiP(Ph)(3)]Fe(OTf) and {[SiP(iPr)(3)]Co(OTf)}{OTf}, suitable for group transfer studies.
  • Comparative analysis of structural, electrochemical, and spectroscopic data for related complexes.

Conclusions:

  • The tris(phosphino)silyl ligand enables the formation of novel coordination complexes with unique structural and electronic properties.
  • These findings expand the scope of dinitrogen coordination chemistry, particularly for monovalent iron complexes.
  • The synthesized triflate complexes hold promise for applications in group transfer reactions.