The synthesis of enantiopure amines via amine transaminases involves several challenges including unfavorable reaction equilibria and product inhibition. Described here is a non‐catalytic approach to overcome such problems by using an in situ‐product crystallization (ISPC) to selectively remove a targeted product amine from an amine transaminase‐catalyzed reaction. The continuous removal of the product amine from its reaction solution as a barely soluble salt effectively yields a displacement of the reaction equilibrium towards the products and facilitates a simple downstream processing approach via filtration. The targeted product amine is eventually obtained from the salt, while the counterion compound can be easily recycled.

We report the synthesis and full characterization of dinuclear complexes with the bridging ligand phenanthroline-5,6-dithiolate (phendt(2-)) featuring the [Ru(bpy)2](2+) or Ir(ppy)2](+) fragment at the diimine donor center and the [Ni(dppe)](2+) or [Pt(phen)](2+) complex moiety at the dithiolate group. The molecular structures of the mononuclear complexes [(C5H5)2Ti(S,S'-phendt)] and [(ppy)2Ir{N,N'-phendt-(C2H4CN)2}](PF6) as well as the dinuclear complex [(C5H5)(PPh3)Ru(phendt)Ni(dppe)](PF6) determined by X-ray diffraction (XRD) studies are compared. Photophysical studies with mononuclear [(bpy)2Ru{phendt-(C2H4CN)2}](2+) and [(ppy)2Ir{phendt-(C2H4CN)2}](+) as well as dinuclear [(bpy)2Ru(phendt)Ni(dppe)](2+) and [(ppy)2Ir(phendt)Ni(dppe)](+) uncovered an effective luminescence quenching in the dinuclear complexes. Lifetime measurements at room temperature, steady-state measurements at low temperature, electrochemical investigations, and DFT calculations provide evidence for a very efficient energy transfer from the Ru/Ir to the Ni complex moiety with a rate constant k > 5 × 10(9) s(-1). In comparison, the [Ru]phendt[Ni] complex displays a higher quenching efficiency with reduced excited state lifetime, whereas the [Ir]phendt[Ni] complex is characterized by an unaltered lifetime of the thermally equilibrated excited state.

A series of heterodinuclear complexes with acetylene dithiolate (acdt(2-) ) as the bridging moiety were synthesised by a facile one-pot procedure that avoided use of the highly elusive acetylene dithiol. Generation of the W-Ru complex [Tp'W(CN)(CO)(C2 S2 )Ru(η(5) -C5 H5 )(PPh3 )] (Tp'=hydrotris(3,5-dimethylpyrazolyl)borate) and the W-Pd complexes [Tp'W(CN)(CO)(C2 S2 )Pd(dppe)] and [Tp'W(CO)2 (C2 S2 )Pd(dppe)][PF6 ] (dppe=1,2-bis(diphenylphoshino)ethane), which exhibit a [W(η(2) -κ(2) -C2 S2 )M] core (M=Ru, Pd), was accomplished by using a transition-metal-assisted solvolytical removal of the Me3 Si-ethyl thiol protecting groups. All intermediate species of the reaction have been fully characterised. The highly coloured W-Ru complex [Tp'W(CN)(CO)(C2 S2 )Ru(η(5) -C5 H5 )(PPh3 )] shows reversible redox chemistry, as does the prototype complex [Tp'W(CO)2 (C2 S2 )Ru(η(5) -C5 H5 )(PPh3 )][PF6 ]. Single crystal X-ray diffraction and IR, EPR and UV/Vis spectroscopic studies in conjunction with DFT calculations prove the high electronic delocalisation of states over the acdt(2-) linker. Comparative studies revealed a higher donor strength and more pronounced dithiolate character of acdt(2-) in [Tp'W(CN)(CO)(C2 S2 )Ru(η(5) -C5 H5 )(PPh3 )] relative to [Tp'W(CO)2 (C2 S2 )Ru(η(5) -C5 H5 )(PPh3 )](+) . In addition, the influence of the overall complex charge on the metric parameters was investigated by single-crystal X-ray diffraction studies with the W-Pd complexes [Tp'WL2 (C2 S2 )Pd(dppe)] (L=(CN(-) )(CO) or (CO)2 ). The central [W(C2 S2 )Pd] units exhibit high structural similarity, which indicates the extensive delocalisation of charge over both metals.