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Bis phenylene flatt...
Bis phenylene flattened 13-membered tetraamide macrocyclic ligand (TAML) for square planar cobalt(III)
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- Ellis, W. Chadwick (författare)
- Carnegie Mellon Univ, Dept Chem, 4400 5th Ave, Pittsburgh, PA 15213 USA.
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- Ryabov, Alexander D. (författare)
- Carnegie Mellon Univ, Dept Chem, 4400 5th Ave, Pittsburgh, PA 15213 USA.
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- Fischer, Andreas C., 1982- (författare)
- KTH,Kemi
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- Hayden, Joshua A. (författare)
- 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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- Shen, Longzhu Q. (författare)
- Carnegie Mellon Univ, Dept Chem, 4400 5th Ave, Pittsburgh, PA 15213 USA.;Univ Cambridge, Dept Zool, Downing St, Cambridge CB2 3EJ, England.
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- Bominaar, Emile L. (författare)
- Carnegie Mellon Univ, Dept Chem, 4400 5th Ave, Pittsburgh, PA 15213 USA.
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- Hendrich, Michael P. (författare)
- Carnegie Mellon Univ, Dept Chem, 4400 5th Ave, Pittsburgh, PA 15213 USA.
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- Collins, Terrence J. (författare)
- Carnegie Mellon Univ, Dept Chem, 4400 5th Ave, Pittsburgh, PA 15213 USA.
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Carnegie Mellon Univ, Dept Chem, 4400 5th Ave, Pittsburgh, PA 15213 USA Kemi (creator_code:org_t)
- 2018-06-29
- 2018
- Engelska.
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Ingår i: Journal of coordination chemistry (Print). - : TAYLOR & FRANCIS LTD. - 0095-8972 .- 1029-0389. ; 71:11-13, s. 1822-1836
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https://urn.kb.se/re...
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https://doi.org/10.1...
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Abstract
Ämnesord
Stäng
- 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] .
Ämnesord
- NATURVETENSKAP -- Kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences (hsv//eng)
Nyckelord
- Macrocyclic complex
- TAML
- cobalt
- radical cation
- EPR
- DFT
Publikations- och innehållstyp
- ref (ämneskategori)
- art (ämneskategori)
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