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dc.contributor.authorKing, Evan Robert
dc.contributor.authorBetley, Theodore A
dc.date.accessioned2017-04-13T16:24:06Z
dc.date.issued2009
dc.identifier.citationKing, Evan R., and Theodore A. Betley. 2009. Unusual electronic structure of first row transition metal complexes featuring redox-active dipyrromethane ligands. Journal of the American Chemical Society 131(40): 14374-14380.en_US
dc.identifier.issn0002-7863en_US
dc.identifier.urihttp://nrs.harvard.edu/urn-3:HUL.InstRepos:32116865
dc.description.abstractTransition metal complexes (Mn f Zn) of the dipyrromethane ligand, 1,9-dimesityl-5,5- dimethyldipyrromethane (dpm), have been prepared. Arylation of the dpm ligand R to the pyrrolic nitrogen donors limits the accessibility of the pyrrole π-electrons for transition metal coordination, instead forcing η1,η1 coordination to the divalent metal series as revealed by X-ray diffraction studies. Structural and magnetic characterization (SQUID, EPR) of the bis-pyridine adducts of (dpm)MnII(py)2, (dpm)FeII(py)2, and (dpm)- CoII(py)2 reveal each divalent ion to be high-spin and pseudotetrahedral in the solid state, whereas the (dpm)NiII(py)2 is low-spin and adopts a square-planar geometry. Differential pulse voltammetry on the (dpm)MII(py)2 series reveals a common two-electron oxidation pathway that is entirely ligand-based, invariant to the divalent metal-bound, its geometry or spin state within the dpm framework. This latter observation indicates that fully populated ligand-based orbitals from the dpm construct lie above partially filled metal 3d orbitals without intramolecular redox chemistry or spin-state tautomerism occurring. DFT analysis on this family of complexes corroborates this electronic structure assignment, revealing that the highest lying molecular orbitals are completely ligand-based. Chemical oxidation of the deprotonated dpm framework results in the four-electron oxidation of the dipyrrolide framework, although this oxidation product was not observed either in the electrochemical or chemical oxidation of the (dpm)MII(py)2 complexes.en_US
dc.description.sponsorshipChemistry and Chemical Biologyen_US
dc.language.isoen_USen_US
dc.publisherAmerican Chemical Societyen_US
dc.relation.isversionofdoi:10.1021/ja903997aen_US
dash.licenseMETA_ONLY
dc.titleUnusual Electronic Structure of First Row Transition Metal Complexes Featuring Redox-Active Dipyrromethane Ligandsen_US
dc.typeJournal Articleen_US
dc.description.versionVersion of Recorden_US
dc.relation.journalJournal of the American Chemical Societyen_US
dash.depositing.authorBetley, Theodore A
dash.embargo.until10000-01-01
dc.identifier.doi10.1021/ja903997a*
workflow.legacycommentsBetley emailed 2016-04-13 AD. Betley emailed 2017-02-16 MM meta.darken_US
dash.contributor.affiliatedKing, Evan
dash.contributor.affiliatedBetley, Theodore


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