A Synthetic Strategy for Cofacial Porphyrin‐Based Homo‐ and Heterobimetallic Complexes. Issue 9 (18th January 2021)

• Record Type: Journal Article
• Authors: Schissler, Christoph; Schneider, Erik K.; Felker, Benjamin; Weis, Patrick; Nieger, Martin; Kappes, Manfred M.; Bräse, Stefan
• Is Part Of: Chemistry. Volume 27:Issue 9(2021)
• Page Start: 3047
• Page End: 3054
• Publication Date: 2021-01-18
• Subjects: active site analogues -- bimetallic complexes -- carbon monoxide dehydrogenase -- ion mobility spectrometry -- porphyrin dimers; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.202002394
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: We present a straightforward and generally applicable synthesis route for cofacially linked homo‐ and heterobimetallic porphyrin complexes. The protocol allows the synthesis of unsymmetrical aryl‐based meso ‐ meso as well as β‐ meso ‐linked porphyrins. Our method significantly increases the overall yield for the published compound known as o ‐phenylene‐bisporphyrin (OBBP) by a factor of 6.8. Besides the synthesis of 16 novel homobimetallic complexes containing Mn III, Fe III, Ni II, Cu II, Zn II, and Pd II, we achieved the first single‐crystal X‐ray structure of an unsymmetrical cofacial benzene‐linked porphyrin dimer containing both planar‐chiral enantiomers of a Ni II 2 complex. Additionally, this new methodology allows access to heterobimetallic complexes such as the Fe III ‐Ni II containing carbon monoxide dehydrogenase active site analogue. The isolated species were investigated by various techniques, including ion mobility spectrometry, DFT calculations, and UV/Vis spectroscopy. This allowed us to probe the influence of interplane distance on Soret band splitting. Abstract : Simple route to dimeric complexes : Three different types of covalently linked metalloporphyrin dimers were synthesized. The monomers were synthesized sequentially and can be filled with metals before linking. As a result, different heterobimetallic systems can be made. Depending on the metals M1 and M2 used (M=Mn, Fe, Ni, Cu, Zn, Pd), a wide range of potentially catalytically active species can be prepared, such as analogues of carbon monoxide dehydrogenase.