Phenanthridine-Containing Pincer-like Amido Complexes of Nickel, Palladium, and Platinum

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Date
2017-03-07
Authors
Mandapati, Pavan
Giesbrecht, Patrick
Davis, Rebecca
Herbert, David E
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Journal ISSN
Volume Title
Publisher
American Chemical Society
Abstract
Proligands based on bis(8-quinolinyl)amine (L1) were prepared containing one (L2) and two (L3) benzo-fused N-heterocyclic phenanthridinyl (3,4-benzoquinolinyl) units. Taken as a series, L1–L3 provides a ligand template for exploring systematic π-extension in the context of tridentate pincer-like amido complexes of group 10 metals (1-M, 2-M, and 3-M; M = Ni, Pd, Pt). Inclusion of phenanthridinyl units was enabled by development of a cross-coupling/condensation route to 6-unsubstituted, 4-substituted phenanthridines (4-Br, 4-NO2, 4-NH2) suitable for elaboration into the target ligand frameworks. Complexes 1-M, 2-M, and 3-M are redox-active; electrochemistry and UV–vis absorption spectroscopy were used to investigate the impact of π-extension on the electronic properties of the metal complexes. Unlike what is typically observed for benzannulated ligand–metal complexes, extending the π-system in metal complexes 1-M to 2-M to 3-M led to only a moderate red shift in the relative highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) gap as estimated by electrochemistry and similarly subtle changes to the onset of the lowest-energy absorption observed by UV–vis spectroscopy. Time-dependent density functional theory calculations revealed that benzannulation significantly impacts the atomic contributions to the LUMO and LUMO+1 orbitals, altering the orbital contributions to the lowest-energy transition but leaving the energy of this transition essentially unchanged.
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Keywords
Coordination Chemistry
Citation
Inorganic Chemistry 2017, 56(6), 3674-3685