A family of SCS and SNS pincer compounds of the type [PdCl{C6H3‐2,6‐(CH2SR)2}] {R = tBu (3a), sBu (3b), iBu (3c)} and [NiCl2{C5H3N‐2,6‐(CH2SR)2}] {R = tBu (4a), sBu (4b)} have been prepared. Among these, complexes 3b, 3c, 4a–4c are reported for the first time. Dimeric compounds such as [NiCl{C5H3N‐2,6‐(CH2SiBu)2}μ‐Cl]2 (4c) were found in the solid state for the nickel complexes with lower steric hindrance exhibiting octahedral metal centers, whereas other nickel structures such as [NiCl2{C5H3N‐2,6‐(CH2StBu)2}(iPrOH)] (4d) could also expand their coordination number by coordinating to solvents. The single crystal X‐ray diffraction results for 4a, 4c and 4d are presented. The catalytic activity of the six compounds was studied in C–C and C–S cross‐coupling reactions under conventional heating and under microwave irradiation conditions. The palladium catalysts enabled good to excellent conversions in Suzuki–Miyaura couplings of p‐substituted halobenzenes with phenylboronic acid. Comparable yields resulted from application of the nickel complexes in the thioetherification of iodobenzene with different disulfides. The fast increase in reaction temperature associated with microwave irradiation, in combination with the robust pincer catalysts, allowed for quantitative conversions in only minutes.

A series of Grubbs-type catalysts that contain lipase-inhibiting phosphoester functionalities have been synthesized and reacted with the lipase cutinase, which leads to artificial metalloenzymes for olefin metathesis. The resulting hybrids comprise the organometallic fragment that is covalently bound to the active amino acid residue of the enzyme host in an orthogonal orientation. Differences in reactivity as well as accessibility of the active site by the functionalized inhibitor became evident through variation of the anchoring motif and substituents on the N-heterocyclic carbene ligand. Such observations led to the design of a hybrid that is active in the ring-closing metathesis and the cross-metathesis of N,N-diallyl-p-toluenesulfonamide and allylbenzene, respectively, the latter being the first example of its kind in the field of artificial metalloenzymes.

A Rh(NHC) phosphonate complex reacts with the lipases cutinase and Candida antarctica lipase B resulting in the first (soluble) artificial metalloenzymes formed by covalent active site-directed hybridization. When compared to unsupported complexes, these new robust hybrids show enhanced chemoselectivity in the (competitive) hydrogenation of olefins over ketones.