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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


(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. 

  • The trans-S--π-System-S- pocket:


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, and Dr. Felix Koch.