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

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dc.contributor.authorMandapati, Pavan
dc.contributor.authorGiesbrecht, Patrick
dc.contributor.authorDavis, Rebecca
dc.contributor.authorHerbert, David E
dc.date.accessioned2021-10-15T19:40:48Z
dc.date.available2021-10-15T19:40:48Z
dc.date.issued2017-03-07
dc.date.submitted2021-10-15T19:39:39Zen_US
dc.description.abstractProligands 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.en_US
dc.description.sponsorshipNatural Sciences and Engineering Research Council of Canada (RGPIN-2014-03733)en_US
dc.identifier.citationInorganic Chemistry 2017, 56(6), 3674-3685en_US
dc.identifier.doi10.1021/acs.inorgchem.7b00075
dc.identifier.other0000-0002-3686-4850
dc.identifier.urihttp://hdl.handle.net/1993/36046
dc.language.isoengen_US
dc.publisherAmerican Chemical Societyen_US
dc.rightsopen accessen_US
dc.subjectCoordination Chemistryen_US
dc.titlePhenanthridine-Containing Pincer-like Amido Complexes of Nickel, Palladium, and Platinumen_US
dc.typePreprinten_US
local.author.affiliationFaculty of Scienceen_US
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