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Bis phenylene flattened 13-membered tetraamide macrocyclic ligand (TAML) for square planar cobalt(III)
Carnegie Mellon Univ, Dept Chem, 4400 5th Ave, Pittsburgh, PA 15213 USA..
Carnegie Mellon Univ, Dept Chem, 4400 5th Ave, Pittsburgh, PA 15213 USA..
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemistry.ORCID iD: 0000-0003-3452-6361
Carnegie Mellon Univ, Dept Chem, 4400 5th Ave, Pittsburgh, PA 15213 USA.;525 East 68th St,Suite F-715, New York, NY 10065 USA..
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2018 (English)In: Journal of coordination chemistry (Print), ISSN 0095-8972, E-ISSN 1029-0389, Vol. 71, no 11-13, p. 1822-1836Article in journal (Refereed) Published
Abstract [en]

The preparation, characterization, and evaluation of a cobalt(III) complex [CO{(OC)2(o,o'-NC6H4NCO)2CMe2}(OH2)]- with 13-membered tetraamide macrocyclic ligand (TAML) is described. This is a square-planar (X-ray) S=1 paramagnetic (H-1 NMR) compound, which becomes an S=0 diamagnetic octahedral species in excess d(5)-pyridine. Its one-electron oxidation at an electrode is fully reversible with the lowest E-1/2 value (0.66V vs SCE) among all investigated Co-III TAML complexes. The oxidation results in a neutral blue species which is consistent with a Co-III/radical-cation ligand. The ease of oxidation is likely due to the two benzene rings incorporated in the ligand structure (whereas there is just one in many other Co-III TAMLs). The oxidized neutral species are unexpectedly EPR silent, presumably due to the -stacking aggregation. However, they display eight-line hyperfine patterns in the presence of excess of 4-tert-butylpyridine or 4-tert-butyl isonitrile. The EPR spectra are more consistent with the Co-III/radical-cation ligand formulation rather than with a Co-IV complex. Attempts to synthesize a similar vanadium complex under the same conditions as for cobalt using [(VO)-O-V(OCHMe2)(3)] were not successful. TAML-free decavanadate was isolated instead. [GRAPHICS] .

Place, publisher, year, edition, pages
TAYLOR & FRANCIS LTD , 2018. Vol. 71, no 11-13, p. 1822-1836
Keywords [en]
Macrocyclic complex, TAML, cobalt, radical cation, EPR, DFT
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:kth:diva-269586DOI: 10.1080/00958972.2018.1487060ISI: 000448334400017Scopus ID: 2-s2.0-85049125211OAI: oai:DiVA.org:kth-269586DiVA, id: diva2:1417670
Note

QC 20200330

Available from: 2020-03-30 Created: 2020-03-30 Last updated: 2020-03-30Bibliographically approved

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Fischer, Andreas C.

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