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Structure-Reactivity Relationship in Transition-Metal Thiolates

Why thiolate?


We aim at making use of the functional properties of M-S bonds which include:

 

  • Covalent bonding: e--Relay

  • Bronsted-basicity: H+-Relay

  • Redox-activity: Thiyl/thiolate mixed-valent structures
  • The trans-S--π-System-S- pocket:
  • (a) Adaptive bonding that suits variable stereoelectronic requirements.
    (b) Control of relative metal-ligand d-p-orbital alignment in square planar metal complexes by additional ligands, e.g. phosphines. 

 

To what effect?


  • Manipulation and synchronisation of redox-properties of metal sites in dinuclear [M2S2]n+ cores significant for:

    (a) H+-reduction
    (b) Hysteresis properties

     

  • d8-Metal-coupled mixed-valent thiyl/thiolate structures:
    (a) Relative metal-ligand d/p-orbital alignment determines degree of charge-delocalisation within
    [ArS-PtII-SAr]+-cores, which results in distinct absorption bands in the near infrared (NIR) spectral region.

 

Who is on the team?

  Dipl. Chem. Nicole Mews, Dr. Andreas Berkefeld und Dipl. Chem. Felix Koch.