The synthesis and antiproliferative activity of Mes-and iPr-substituted gold(I) bis(1,2,3-triazol-5-ylidene) complexes in various cancer cell lines are reported, showing nanomolar IC 50 values of 50 nM (lymphoma cells) and 500 nM (leukemia cells), respectively (Mes < iPr). The compounds exclusively induce apoptosis (50 nM to 5 μM) instead of necrosis in common malignant blood cells (leukemia cells) and do not affect non-malignant leucocytes. Remarkably, the complexes not only overcome resistances against the well-established cytostatic etoposide, cytarabine, daunorubicin, and cisplatin but also promote a synergistic effect of up to 182% when used with daunorubicin. The present results demonstrate that gold(I) bis(1,2,3-triazol-5-ylidene) complexes are highly promising and easily modifiable anticancer metallodrugs.

The mixed acetate acetylacetonate (acac) ruthenium(II) phosphine complexes Ru(OAc)(acac)P2 [P2=(PPh3)2, Ph2P(CH2)4PPh2 (dppb)] were prepared by protonation of Ru(OAc)2(PPh3)2 with acetylacetone in dichloromethane. Reaction of the dppb derivative with 2‐(aminomethyl)pyridine (ampy) affords the complex Ru(OAc)(acac)(ampy)(dppb), which converts to [Ru(acac)(ampy)(dppb)](OAc) in toluene at 90 °C. In the former derivative the ampy ligand is monodentate and coordinates through the NH2‐moiety. The isolated acac complexes are active catalysts for the transfer hydrogenation of ketones with loadings as low as 0.01 mol%, the ampy having a strong accelerating effect. Several aromatic and aliphatic ketone substrates are converted to their corresponding alcohols, and different electronic influences through substituents on acetophenone are tolerated.

The synthesis of trans axially substituted mono-(1 a) and bis(tert-butylisocyanide) (1 b) derivatives of the highly active homogeneous bio-inspired iron(II) olefin epoxidation (pre-)catalyst 1 bearing an equatorial macrocyclic tetra N-heterocyclic carbene and two trans axial labile acetonitrile ligands is reported. NMR spectroscopy and SC-XRD indicate a considerable π-backdonation from the iron(II) centres to the isocyanide ligand(s). The impact of isocyanide substitution on the electronic features of the complexes is studied by cyclic voltammetry revealing a significant increase in half-cell potential assignable to the reversible Fe(II)/Fe(III) redox couple with an increasing number of isocyanides as a result of their π-accepting properties: E 1/2 = 0.15 V (1), E 1/2 = 0.35 V (1 a), E 1/2 = 0.44 V (1 b).

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The performance of trans axially substituted mono‐(2 a) and bis(tert‐butylisocyanide) (2 b) complexes derived from the highly active bio‐inspired iron(II) (pre‐ )catalyst 2 containing an equatorial macrocyclic tetra N‐heterocyclic carbene in homogenous olefin epoxidation catalysis is reported. H2O2 is used as oxidant in combination with the Lewis acid Sc(OTf)3 as additive resulting in a considerable improvement of catalytic activity. In contrast to other iron epoxidation catalysts, the introduction of π‐accepting isocyanide ligands does not improve the catalytic performance of 2 a and 2 b posed by cyclic voltammetry. However, besides their lower activity, a high temperature tolerance of both compounds is found as a unique feature for iron NHC epoxidation catalysts.