Abstract
The incorporation of donor-type substituents on the allene core opens up the possibility of coordination complexes in which the metal is bonded to the donor groups, with or without interaction with the double bond system. Despite the challenges in the synthesis of such allene-containing metal complexes, their unique 3D environments and dual functionality (allene and metal) could facilitate catalysis and interaction with chemical and biological systems. Bis(pyridyl)allenes are presented here as robust ligands for novel Pd(II), Pt(IV) and Au(III) complexes. Their synthesis, characterisation and first application as catalysts of benchmark reactions for Pd, Pt and Au are presented with interesting reactivity and selectivities. The complexes have also been probed as antimicrobial and anticancer agents with promising activities, and the first studies on their unusual interaction with several DNA structures will open new avenues for research in the area of metallodrugs with new mechanisms of action.
Highlights
We achieved the racemic synthesis of bis( pyridyl)allene ligands 1a–b (Fig. 3b) according to modified literature procedures
Pd, Pt and Au are versatile metals in important catalytic processes, so there is ample data to compare with the state-of-the art metal complexes in those transformations.[29,30,31,32]
Further tuning of the catalyst design is needed to increase the activity with more challenging substrates, we present here the first example of an allene-derived catalytic system used in such an important process that could open further research and developments in the asymmetric version
Summary
The development of ligand architectures with novel 3D arrangements is an important challenge in organic synthesis[1,2,3,4] with implications in the field of catalysis (and asymmetric catalysis), and in the discovery of new organometallic complexes with potential for biological applications, currently an area of increasing growth.[5,6,7]In this context, organic molecules displaying axial chirality, like biaryls or spiranes, have proven to be privileged structures in catalysis and have revolutionised the field of asymmetric catalysis.[8,9,10] despite progress in the field, it is still necessary to develop new chiral ligands to overcome limitations of established catalytic systems in terms of substrate scope, catalytic loading, turnover or enantioselectivity. We report the synthesis and characterisation of Pd(II), Pt (IV) and Au(III) bis( pyridyl)allene-containing complexes, and the explorative exploitation of their unique structures as catalysts and as potential metallodrugs in three settings, as antimicrobial agents, as anticancer drugs and their specific interaction with different structures of DNA.
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